Conversion of 2,3-butanediol to butadiene

ABSTRACT

A composition comprising 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by exposure to a catalyst comprising (a) M x O y  wherein M is a rare earth metal, a group IIIA metal, Zr, or a combination thereof, and x and y are based upon an oxidation state of M, or (b) M 3   a (PO 4 ) b  where M 3  is a group IA, a group IIA metal, a group IIIA metal, or a combination thereof, and a and b are based upon the oxidation state of M 3 . Embodiments of the catalyst comprising M x O y  may further include M 2 , wherein M 2  is a rare earth metal, a group IIA metal, Zr, Al, or a combination thereof. In some embodiments, 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by a catalyst comprising M x O y , and the methyl vinyl carbinol is subsequently dehydrated to 1,3-butadiene by exposure to a solid acid catalyst.

CROSS-REFERENCE TO RELATED APPLICATION

This claims the benefit of the earlier filing date of U.S. ProvisionalApplication No. 61/935,050, filed Feb. 3, 2014, which is incorporated byreference in its entirety herein.

ACKNOWLEDGMENT OF GOVERNMENT SUPPORT

This invention was made with government support under DE-AC05-76RL01830awarded by the United States Department of Energy. The government hascertain rights in the invention.

FIELD

This disclosure concerns embodiments of catalysts and a method forconverting 2,3-butanediol to 1,3-butadiene.

BACKGROUND

1,3-Butadiene (1,3BD) is an important industrial chemical. 1,3-Butadieneis a major component of synthetic rubber, ABS(acrylonitrile-butadiene-styrene terpolymer), and latex. It is animportant intermediate in production of the nylon intermediatesadiponitrile and hexamethylenediamine. 1,3-Butadiene is also used tomake higher value chemicals, such as cycloalkanes, cycloalkenes,1-octene chloroprene, sulfolane, 4-vinylcyclohexene, cyclooctadiene, andcyclododecatriene. Vinylcyclohexene, for example, can be converted tostyrene, which has a market of about 20 billion pounds (about 9 billionkg) per year. 1,3-Butadiene is an important co-monomer of polyethylenewith a market size of over 1 billion pounds (over 450 million kg) peryear. 1,3BD also can be oligomerized to form dimers, trimers, andtetramers that are useful as fuel components.

2,3-Butanediol (BDO), which may be generated as a product in somefermentation and thermochemical systems, can be used for production ofbio-renewable 1,3BD. However, known methods for converting BDO to 1,3BDsuffer from several disadvantages, including corrosive reagents,radioactive catalysts, and/or undesirable products. For example, BDO canbe esterified with acetic acid to the diacetate, followed by pyrolysisof the diacetate to 1,3BD (Morell, Industrial and Engineering Chemistry,37(9):877-884, 1945). This approach is complicated by the corrosivenature of the acetic acid produced, which necessitates special materialsof construction.

A secondary route to 1,3BD starting with BDO is through 2-butenes, whichare available either from 2-butanol by dehydration or from the1,3-dioxolanes by acid catalyzed thermolysis. The butenes can becatalytically dehydrogenated to 1,3BD in the presence of superheatedsteam as diluent and heating medium (Kearby, The chemistry of petroleumhydrocarbons, ed. B. T. Brooks et al., Vol. 2., Reinhold, N.Y., 1955).

Dehydration of BDO is another route to 1,3BD. Dehydration of BDO canproceed by different mechanisms depending upon the catalyst used. Overmany catalysts, including catalysts that are Brønsted acids (e.g.,alumina, acidic zeolites), the product is methyl ethyl ketone (MEK).

SUMMARY

A feed stream including 2,3-butanediol (BDO) is converted to methylvinyl carbinol (MVC) and/or 1,3-butadiene (1,3BD) by exposure to acatalyst comprising (a) M_(x)O_(y) wherein M is a rare earth metal, agroup IIIA metal, Zr, or a combination thereof, and x and y are basedupon an oxidation state of M, or (b) M³ _(a)(PO₄)_(b) where M³ is agroup IA, a group IIA metal, a group IIIA metal, or a combinationthereof, and a and b are based upon the oxidation state of M³. In someembodiments, the catalyst further includes a dopant M², wherein M² is arare earth metal, a group IA metal, a group IIA metal, a group IIIAmetal, Zr, or a combination thereof, and wherein M² is different than Mor M³. In any or all of the above embodiments, the catalyst may be (i)an oxide of In, Al, La, and Zr, (ii) an oxide of Al and Zr, (iii) anoxide of Zr and Ca, (iv) Tm₂O₃, (v) ZrO₂, (vi) Sc₂O₃, or (vii) In₂O₃. Inany or all of the above embodiments, the catalyst may have a MVCselectivity of at least 20%, a 1,3BD selectivity of at least 20%, or acombined 1,3BD and MVC selectivity of at least 20%. In any or all of theabove embodiments, the composition may comprise at least 5 wt % BDO. Inany or all of the above embodiments, the catalyst may dehydrate at least5% of the BDO.

In any or all of the above embodiments, the BDO feed stream may becontacted with the catalyst at a temperature within a range of 250° C.to 700° C., such as a temperature of 250° C. to 400° C. In someembodiments, the feed stream is contacted with the catalyst at ambientpressure.

In any or all of the above embodiments, the feed stream may be contactedwith the catalyst by flowing the feed stream over the catalyst orthrough a catalyst bed comprising the catalyst at a flow rate effectiveto produce a W/F (catalyst weight (g)/feed flow rate (mol/h)) valuewithin a range of 0.5 to 100 g catalyst·h/mol feed stream, such as a W/Ffrom 1 to 10 g catalyst·h/mol feed stream. In some embodiments, the feedstream is flowed through a column containing the catalyst at a weighthourly space velocity (WHSV) from 0.3 to 12 h⁻¹, such as a WHSV from 3to 8 h⁻¹. In certain embodiments, the catalyst is capable of dehydratingat least 5 wt % of the BDO for at least 200 minutes at a temperature of250-400° C. and a mass hourly space velocity from 3 to 8 h⁻¹.

When the product includes MVC, the method may further comprisecontacting the product with a solid acid catalyst and dehydrating theMVC to form a subsequent product comprising 1,3BD. Exemplary solid acidcatalysts include silicoaluminate, alumina, and sulfated zirconia.

In some embodiments, BDO is converted to 1,3BD by (i) contacting a BDOcomposition with a first catalyst maintained at a temperature within arange of 250° C. to 700° C., wherein the first catalyst comprisesM_(x)O_(y) as described above; (ii) dehydrating at least 5 wt % of theBDO with the first catalyst to form a product including MVC, 1,3BD, or acombination thereof; (iii) subsequently contacting the product with asecond catalyst comprising a solid acid catalyst maintained at atemperature with a range of 250° C. to 700° C.; and (iv) dehydrating atleast 5% of the MVC with the solid acid catalyst to form a subsequentproduct comprising 1,3BD. In some examples, the first catalystdehydrates at least 50 wt % of the BDO. The first catalyst may have aMVC selectivity of at least 50%. The BDO composition may be contactedwith the first catalyst at a temperature in the range of 250° C. to 400°C. The product may be contacted with the solid acid catalyst at atemperature in the range of 250° C. to 400° C.

In any or all of the above embodiments, each of the first catalyst andthe second catalyst may be provided in a catalyst bed. In someembodiments, each of the first catalyst and the second catalyst isdisposed in a column. In one embodiment, the first catalyst is disposedin a first column, and the solid acid catalyst is disposed in a secondcolumn fluidly connected to the first column. In another embodiment, thefirst catalyst bed and the second catalyst bed are disposed serially ina single column such that the composition is contacted with the firstcatalyst and subsequently is contacted with the solid acid catalyst. Inyet another embodiment, the first catalyst bed and the second catalystbed are combined to form a mixed catalyst bed comprising the firstcatalyst and the solid acid catalyst. In any or all of the aboveembodiments, the BDO composition and/or the MVC-containing product maybe flowed through the column(s) at a flow rate effective to produce aW/F (catalyst weight (g)/feed flow rate (mol/h)) value within a range of0.5 to 100 g catalyst·h/mol feed stream. In any or all of the aboveembodiments, the first catalyst may be In₂O₃. In any or all of the aboveembodiments, at least 50% of the BDO may be dehydrated with the firstcatalyst.

The foregoing and other objects, features, and advantages of theinvention will become more apparent from the following detaileddescription, which proceeds with reference to the accompanying figures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a process flow diagram of a continuous, fixed-bed flowreactor, as used in Example 3.

FIG. 2 is a process flow diagram of a continuous, fixed-bed flowreactor, as used in Example 4.

DETAILED DESCRIPTION

This disclosure concerns embodiments of catalysts and methods fordehydrating 2,3-butanediol to form 1,3-butadiene. As used herein,dehydration refers to a reaction that removes H₂O from an alcohol toform an alkene. A diol, such as 2,3-butanediol may be partiallydehydrated by removing one H₂O molecule, or completely dehydrated byremoving two H₂O molecules. Thus the term “dehydration” may refer topartial or complete dehydration of 2,3-butanediol. As shown below, BDOis initially dehydrated to methyl vinyl carbinol (MVC). MVC may befurther dehydrated to form 1,3BD.

The conventional catalyst for forming 1,3BD is radioactive thoria(ThO₂), reported by M. E. Winfield (J. Coun. Sci. Industr. Res. Aust.,18, 412-23, 1945; Australian Journal of Scientific Research Seriesa-Physical Sciences 3(2): 290-305, 1950). In the presence of waterformed by the dehydration reaction, however, activity may be retardedand conversion may be incomplete. A common undesirable side product ofthe reaction is methyl ethyl ketone (MEK). Thus, a need exists for anon-radioactive catalyst and method for making 1,3BD from BDO.

I. DEFINITIONS AND ABBREVIATIONS

The following explanations of terms and abbreviations are provided tobetter describe the present disclosure and to guide those of ordinaryskill in the art in the practice of the present disclosure. As usedherein, “comprising” means “including” and the singular forms “a” or“an” or “the” include plural references unless the context clearlydictates otherwise. The term “or” refers to a single element of statedalternative elements or a combination of two or more elements, unlessthe context clearly indicates otherwise.

Unless explained otherwise, all technical and scientific terms usedherein have the same meaning as commonly understood to one of ordinaryskill in the art to which this disclosure belongs. Although methods andmaterials similar or equivalent to those described herein can be used inthe practice or testing of the present disclosure, suitable methods andmaterials are described below. The materials, methods, and examples areillustrative only and not intended to be limiting. Other features of thedisclosure are apparent from the following detailed description and theclaims.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, percentages, and soforth, as used in the specification or claims are to be understood asbeing modified by the term “about.” Unless otherwise indicated,non-numerical properties, such as anhydrous, as used in thespecification or claims are to be understood as being modified by theterm “substantially,” meaning to a great extent or degree. Accordingly,unless otherwise indicated, implicitly or explicitly, the numericalparameters and/or non-numerical properties set forth are approximationsthat may depend on the desired properties sought, limits of detectionunder standard test conditions/methods, limitations of the processingmethod, and/or the nature of the parameter or property. When directlyand explicitly distinguishing embodiments from discussed prior art, theembodiment numbers are not approximates unless the word “about” isrecited.

1,3BD: 1,3-butadiene

BDO: 2,3-butanediol

Calcine: As used herein, the term “calcine” means to heat a solid to atemperature below its melting point to bring about a state of thermaldecomposition, remove crystalline waters of hydration, change thecatalyst or support crystal structure, change the catalyst crystallitesize, and/or to oxidize some metals.

Catalyst: A substance that increases the rate of a chemical reactionwithout itself being consumed or undergoing a chemical change. Acatalyst also may enable a reaction to proceed under differentconditions (e.g., at a lower temperature) than otherwise possible.

Dopant: As used herein, dopant refers to an element added to a catalyst,to alter the catalyst's properties. A dopant may, for example, alter theacidity, catalytic activity, and/or stability (e.g., the activelifetime) of the catalyst.

MEK: methyl ethyl ketone

MVC: methyl vinyl carbinol, 3-buten-2-ol

Rare earth metal: As defined by IUPAC, rare earth metals include thefifteen lanthanides plus scandium and yttrium. Accordingly, rare earthmetals include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er,Tm, Yb, and Lu.

SCCM: standard cubic centimeters per minute

Selectivity: As used herein, selectivity refers to the ability of acatalyst to direct a reaction to preferentially form a particularproduct. For example, suppose a catalyst can dehydrate compound A toform compound B, compound C, or a mixture of compounds B and C. If thecatalyst has a compound B selectivity of 90%, compound A will bedehydrated to form 90% compound B and 10% compound C. Selectivity may bedetermined by analysis of the products formed by the reaction. Incertain examples herein, selectivity was determined by gaschromatography/mass spectrometry of reaction products.

Solid acid catalyst: A solid catalyst including Brønsted acid (protondonor) and/or Lewis acid (electron-pair acceptor) sites, e.g., catalystsincluding protons or acidic groups, such as sulfonic acid groups. Solidacid catalysts include, but are not limited to, acidic zeolites (e.g.,H-ZSM-5, modenite, Y-zeolite), montmorillonite, kaolinite, aluminas,silicas, aluminosilicates, sulfated zirconia, heteropolyacids, metaloxides, metal salts such as metal sulfides, metal sulfates, metalsulfonates, metal nitrates, metal phosphates, metal phosphonates, metalmolybdates, metal tungstates, and certain cation exchange resins (e.g.,cation exchange resins that are stable at the operating temperatures).

W/F: A ratio of catalyst weight to feed flow rate:

W/F=(grams catalyst×hours)/(total moles fed)

WHSV: Weight hourly space velocity. WHSV is defined as the mass of BDOflowing per mass of catalyst per hour.

Zeolite: The term “zeolite” refers to any one of a group of crystallinemicroporous aluminosilicates. Some zeolites include cations (e.g., H⁺,group IA cations or IIA cations) in the pores. Acidic zeolites includeH⁺ cations. Zeolites are often referred to as molecular sieves sincethey can be used to selectively sort molecules by size based on sizeexclusion from the pores. Zeolites may be characterized by pore sizeand/or by the Si/AI ratio. H-ZSM-5 is an exemplary acidic zeolite havingmedium-size pores with channels defined by 10-membered rings ofalternating silicon (or aluminum) and oxygen atoms. For example, H-ZSM-5may have a high Si⁴⁺/Al³⁺ ratio (e.g., 20-30) with a proton for eachAl³⁺ cation to keep the material charge neutral.

II. CATALYSTS

Some embodiments of the disclosed catalysts for converting BDO to MVCand/or 1,3BD have a general formula M_(x)O_(y) wherein M is a rare earthmetal (i.e., Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,Yb, Lu), a group IIIA metal (i.e., In, Ga), zirconium, or a combinationthereof, and x and y have values based upon the oxidation state of M.For example, if M has an oxidation state of 3+, x will be 2 and y willbe 3, e.g., In₂O₃. Similarly, if M has an oxidation state of 4+, x willbe 1 and y will be 2, e.g., ZrO₂. In some embodiments, the catalyst isnot Ceo₂. In certain embodiments, M is In, Sc, La, Tm, Zr, or acombination thereof. In some instances, the catalysts include waters ofhydration, e.g., Zr(OH)₄—Ca(OH)₂ (or Zro₂.2H₂O—CaO.H₂O), Zr(OH)₄ (orZro₂.2H₂O). In other examples, the catalysts are calcined before use andare substantially anhydrous when first contacted with feed. Catalystsmight become more or less hydrated with use.

In certain embodiments, the catalyst further comprises M², wherein M² isa rare earth metal, a group IA, IIA or IIIA metal, Zr, or a combinationthereof, and wherein M² is different than M. M² may be a dopant, such asa dopant present in an amount less than or equal to 20 mol %, ≦15 mol %,≦10 mol %, or ≦5 mol %. In some instances, M² may be a basic metal suchas a Group IIA metal, e.g., calcium, such as Ca-doped ZrO₂. A basicmetal may reduce the number of Brønsted acid sites on the catalystand/or introduce oxygen deficiencies, thereby increasing the catalystselectivity towards forming MVC and/or 1,3BD rather than MEK. The MVCsubsequently is dehydrated to form 1,3BD. M² also may stabilize thecatalyst (such as by reducing degradation) and/or increase itsreactivity, thereby increasing the catalyst lifetime and/or increasingthe yield of MVC and/or 1,3BD.

Metal phosphate catalysts also may be suitable for converting BDO to MVCand/or 1,3BD. In some embodiments, the metal phosphate catalysts have ageneral formula M³ _(a)(PO₄)_(b) where M³ is a group IA, a group IIAmetal, a group IIIA metal, or a combination thereof, and a and b havevalues based upon the oxidation state of M³. For example, when M³ has anoxidation state of 2+, a is 3 and b is 2, e.g., Mg₃(PO₄)₂. In someembodiments, M³ is Ba, Li, Ca, Mg, B, or a combination thereof.Exemplary phosphate catalysts include Ba₃(PO4)₂, LiCaPO₄, BPO₄, andMg₃(PO4)₂. In certain embodiments, a metal phosphate catalyst furthercomprises a dopant M², where M² is as described above.

In some embodiments, the catalyst is (i) an oxide of In, Al, La, and Zr,(ii) an oxide of Al and Zr, (iii) an oxide of Zr and Ca, (iv) Tm₂O₃, (v)ZrO₂, (vi) Sc₂O₃ or (vii) In₂O₃. In certain examples, the catalyst isIn₂O₃.

The catalyst may be disposed on a support, such as a non-acidic support(i.e., a support that has a relatively fewer number Brønsted and/orLewis acid sites compared to Brønsted and/or Lewis base sites). Suitablenon-acidic supports include low-alumina silicas and carbons. The supportmay itself be a catalyst, such as zirconia. For example, Tm₂O₃ may bedisposed on a zirconia support. In addition, the catalyst may bedisposed on the support such that the support never contacts the feed(i.e., an “egg-shell” type catalyst that substantially completely coversthe support), allowing broader selection of useful support materials.

Catalyst reactivity may be affected by particle size and/or surfacearea. In some instances, increasing a catalyst's surface area increasesthe catalyst's reactivity and the 1,3BD and/or MVC yield. Thus, thecatalyst may be comminuted to reduce its particle size and increase itssurface area. In some embodiments, the catalyst has an average particlesize less than 0.5 mm, such as an average particle size from 0.05 mm to0.5 mm, 0.1 mm to 0.5 mm, or 0.1 mm to 0.25 mm. The catalyst may have asurface area of at least 50 m²/g or at least 100 m²/g, such as a surfacearea from 50 m²/g to 1000 m²/g, from 100 m²/g to 750 m²/g, from 100 m²/gto 600 m²/g, or from 300 m²/g to 600 m²/g.

Embodiments of the disclosed catalysts have an MVC and/or 1,3BDselectivity of at least 20%, such as at least 30%, at least 40%, atleast 50%, at least 60%, or at least 70%.

III. CATALYST SYNTHESIS

Some embodiments of the disclosed metal oxide catalysts are prepared bythermal decomposition of their hydrated nitrate or oxalate salts. Ahydrated nitrate salt is heated at or above its decompositiontemperature for a period of time effective to produce a metal oxide. Incertain examples, catalysts were prepared by thermal decomposition oftheir hydrated nitrate salts at temperatures ranging from 450° C. to850° C.; typically, the nitrate salt was heated for 2 hours. In someembodiments, a metal oxide catalyst is prepared by forming a metaloxalate precursor and then thermally decomposing the metal oxalate toproduce metal oxide.

Other metal oxide catalysts can be prepared by depositing a metal oxideonto a support. In some examples, a metal nitrate was combined withhydrous zirconia (denoted as Zr(OH)₄, ZrO(OH)₂, or ZrO₂.2H₂O) andammonia was added to precipitate the metal onto the zirconia. The solidswere dried to form a metal oxide on dried Zr(OH)₄. In other examples, ametal nitrate was combined with calcined zirconia (ZrO₂), and ammoniawas added to precipitate the metal. The solids were calcined to form ametal oxide on calcined zirconia.

Doped metal oxide catalysts can be made by combining nitrate salts indesired amounts and forming metal oxides by any of the above methods. Inone example, a calcium-doped Lu₂O₃ catalyst was formed by combininglutetium and calcium nitrate salts with oxalic acid to form an oxalateprecursor, which was dried and calcined at 550° C. for 6 hours toproduce the calcium-doped Lu₂O₃ catalyst.

In one embodiment, a HfO₂ catalyst was prepared by precipitating thehydrous oxide from a solution of hafnium chloride using aqueous ammonia,and then drying and calcining the solid at 600° C. In anotherembodiment, a ZnO/SiO₂ catalyst was prepared by mixing a zinc nitratesolution with a silica sol, drying the mixture, and calcining theresulting solids at 600° C. for 2 hours. In still another embodiment, amixed oxide of aluminum and zinc was prepared by a co-precipitationprocedure. A first solution containing dissolved ammonium carbonate wasadded to a second solution containing dissolved aluminum nitrate andzinc nitrate. The resulting precipitate was washed, then dried andcalcined at 600° C. for 2 hours.

Embodiments of the disclosed phosphate catalysts can be prepared bydissolving a metal salt in water, and then adding the solution dropwiseto a solution of aqueous ammonium phosphate. The precipitated metalphosphate is washed, dried (e.g., under vacuum), and ground to produce apowder.

IV. METHODS FOR CONVERTING BDO TO MVC AND/OR 1,3BD

Embodiments of the disclosed catalysts are capable of dehydrating BDO toform MVC and/or 1,3BD. A feed stream including BDO is contacted with thecatalyst. The feed stream may comprise at least 5 wt % BDO, such as from5 wt % to 100 wt % BDO. In some embodiments, the feed stream is anaqueous composition comprising BDO. BDO may be obtained from any source.For example, BDO may be obtained as a byproduct of CO fermentation, abyproduct of anaerobic microbial saccharide (e.g., glucose, lactose,galactose) fermentation, or by any other fermentive or thermal process.All isomers of BDO may be used, i.e., d-, l-, and meso isomers.

BDO is exposed to the catalyst by bringing the feed stream comprisingBDO, in liquid or gas phase, into contact with the catalyst for aneffective period of time at an effective temperature and pressure fordehydration to occur as discussed below. BDO may be contacted with thecatalyst by any suitable means, including combining BDO and the catalystin a closed vessel, or flowing BDO across and/or through a catalyst bed,such as a catalyst bed disposed in a column.

At least 3% of the BDO is dehydrated by the catalyst to form a productcomprising MVC, 1,3BD, or a mixture thereof. By “at least 3%” is meantat least 3% of an initial mass or concentration of BDO in the feedstream prior to contact with the catalyst. A person of ordinary skill inthe art understands that a percentage of the initial mass orconcentration may be a weight percent, a mole percent, or even a volumepercent. For example, if the feed stream comprises 10 wt % BDO, at least3% dehydration forms a product comprising no more than 9.7 wt % BDO. Insome embodiments, the catalyst is capable of dehydrating at least 5%, atleast 10%, at least 30%, at least 50%, at least 70%, at least 75%, atleast 90%, or even at least 95% of the BDO to form a product comprisingMVC and/or 1,3BD. When the product comprises MVC, the product may becontacted with a subsequent catalyst to further dehydrate the MVC andform 1,3BD.

The feed stream may be contacted with the catalyst at a temperaturewithin a range of 250-700° C., 250-500° C., 250-400° C., 300-450° C., or300-350° C. The feed stream may be contacted with the catalyst at apressure within a range of 50 mm (6.7 kPa) to 50 atmospheres (5.1 MPa).In some embodiments, the feed stream is contacted with the catalyst atatmospheric pressure. In other embodiments, the feed stream is contactedwith the catalyst at a pressure less than atmospheric pressure, such asa pressure within a range of 50 mm (6.7 kPa) to 750 mm (100 kPa).Reduced pressure may reduce contact time, e.g., by facilitating removalof products from the catalyst surface. In some embodiments, reducingcontact time facilitates conversion to MVC and/or 1,3BD withoutformation of undesirable byproducts, e.g., condensation products. Inother embodiments, the feed stream is contacted with the catalyst at apressure higher than atmospheric, such as a pressure within a range of 1atm (0.1 MPa) to 50 atm (5.1 MPa).

In some embodiments, dehydration is a continuous or substantiallycontinuous process in which a BDO feed stream flows across or through acatalyst bed. For example, a column containing a packed catalyst bed isprepared, and a BDO feed stream is flowed through the column. Thecatalyst in the column is heated to an effective temperature, e.g., witha range of 250° C. to 700° C. In some embodiments, a partial vacuum isapplied to the column so that the column operates at a pressure lessthan atmospheric pressure. In other embodiments, the column is operatedat ambient, or atmospheric, pressure. In still other embodiments, thecolumn is operated at a pressure greater than atmospheric pressure.

In some embodiments, the BDO feed stream is introduced into the columnat ambient temperature. Alternatively, the BDO feed stream may bepreheated to a desired reaction temperature before flowing into thecolumn.

A person of ordinary skill in the art will appreciate that BDO feedstream flow rates through the column are affected by a number ofvariables including, but not limited to, catalyst composition, columndimensions, temperature, pressure, BDO concentration, and combinationsthereof. The BDO feed stream may have a weight hourly space velocity(WHSV) within a range of 0.3 to 12 h⁻¹, such as 0.5 to 12 h⁻¹, 1 to 10h⁻¹, 2 to 9 h⁻¹, 3 to 8 h⁻¹, 4 to 7 h⁻¹, or 5 to 6 h⁻¹. In someexamples, the WHSV was within a range of 5 to 6 h⁻¹.

A carrier gas may flow concurrently through the column with the BDO feedstream. Suitable gases include inert gases (e.g., nitrogen, helium,argon), hydrogen, air, and combinations thereof. In some examples, thegas was nitrogen or helium. The carrier gas flow rate is affected by anumber of variables including, but not limited to catalyst composition,column dimensions, temperature, pressure, BDO concentration, andcombinations thereof.

The carrier gas flow rate and/or BDO feed stream flow rate are selectedto achieve a desired contact time. In some embodiments, flow rates arechosen to attain W/F (catalyst weight/feed flow rate) values in a rangeof 0.5 to 100 g catalyst·h/mol feed stream, such as from 0.5 to 50, from1 to 25, or from 1 to 10 g catalyst·h/mol feed stream.

In some embodiments, the column is purged with the carrier gas beforethe BDO feed stream is introduced into the column. The column may beheated during the carrier gas purge to regenerate the catalyst, e.g., byremoving adsorbed water and/or by-products (e.g., oligomericcondensation products) adsorbed during prior use.

A chilled receiver vessel may be fluidly connected to a distal end ofthe column so that product exiting the column is chilled and condensedto a liquid. Alternatively, products may be collected by adsorption ontoa suitable adsorbent (e.g., a Carbopack™ (graphitized carbon) bed) ortrapping in a solvent (e.g., diglyme) at a reduced temperature (e.g.,less than 50° C.), and subsequently released by heating the adsorbent orsolvent.

Some embodiments of the disclosed catalysts, when contacted with a BDOfeed stream, remain capable of dehydrating at least 5% of the BDO in thefeed stream for at least 200 minutes, at least 300 minutes, or at least500 minutes at a temperature of 250-400° C. and a WHSV of 3-8 h⁻¹. Incertain embodiments, the disclosed catalyst when contacted with a BDOfeed stream remains capable of dehydrating at least 5% of the BDO in thefeed stream for at least 500 minutes at a temperature of 250-350° C. anda WHSV of 5 to 6 h⁻¹.

In some embodiments, the primary product is methyl vinyl carbinol. Forexample, In₂O₃ is a catalyst that selectively converts BDO to MVC. Insome examples, In₂O₃ converts BDO to MVC with an MVC product selectivityof at least 50%, at least 60%, or at least 70%.

A product comprising MVC (MVC composition) may be contacted with asubsequent catalyst that is capable of further dehydrating MVC to form1,3BD. Suitable catalysts for dehydrating MVC include solid acidcatalysts including, but not limited to, aluminosilicates (e.g.,zeolites), alumina, and sulfated zirconia. The MVC composition may becontacted with the solid acid catalyst at a temperature within a rangeof 250-700° C., 250-500° C., 250-400° C., 300-450° C., or 300-350° C.The MVC composition may be contacted with the solid acid catalyst at apressure within a range of 50 mm (6.7 kPa) to 50 atmospheres (5.1 MPa).In some embodiments, the MVC composition is contacted with the catalystat atmospheric pressure. In other embodiments, the MVC composition iscontacted with the catalyst at a pressure less than atmosphericpressure, such as a pressure within a range of 50 mm (6.7 kPa) to 750 mm(100 kPa). In some embodiments, the catalyst dehydrates at least 5% ofthe methyl vinyl carbinol (i.e., at least 5% of an initial mass orconcentration of MVC present in the MVC composition prior to contactwith the catalyst) to form a second product comprising 1,3-butadiene.

Dehydration with a solid acid catalyst may be a continuous orsubstantially continuous process in which a composition comprising MVCflows across or through a catalyst bed. For example, a column containinga packed catalyst bed is prepared, and a composition comprising MVC isflowed through the column. The MVC composition may be introduced intothe column at ambient temperature, or the MVC composition may bepreheated before flowing into the column. A carrier gas may flowconcurrently through the column with the MVC composition.

In some embodiments, the solid acid catalyst is disposed in a secondcolumn downstream from a first column that includes a first catalystcapable of dehydrating BDO to form a product comprising MVC. The firstand second columns may be operated under the same or differentconditions (e.g., temperature, WHSV, W/F, carrier gas, pressure, etc.)In one embodiment, the columns are in fluid communication such that afirst product comprising MVC exits via an outlet of the first column andflows directly into the second column via an inlet of the second column.

In another embodiment, the first catalyst and the solid acid catalystare disposed within a single column such that, for example, a first zonewithin the column contains the first catalyst bed and a second,downstream zone within the column contains the solid acid catalyst bed.The zones may be at the same or different temperatures. In still anotherembodiment, the first catalyst and the solid acid catalyst are mixed toform a mixed catalyst bed within a single column.

V. EXAMPLES Materials

Methyl ethyl ketone (99+%) and 2,3-butanediol were obtained from AldrichChemical Co. The Aldrich BDO (98%) was a mixture of meso- (˜76%) andracemic d/l isomers (˜24%). BDO obtained from LanzaTech was a d/lmixture (˜95%) and contained very little meso isomer (˜3%).

Pyroprobe GC/MS Apparatus

The pyroprobe unit used in this work was a CDS Analytical, Inc. Series5000 pyroprobe (model 5200). The pyroprobe was equipped with anoptionally used downstream heated catalyst bed, and a heated Carbopackadsorbent bed located between the catalyst bed and the gas chromatograph(GC) inlet. The GC used was an Agilent Technologies 7890A GC system,equipped with an Agilent Technologies 5975C inert XL mass spectroscopic(MS) detector with Triple-Axis Detector. The GC column used for productseparation was a DB5 column.

Catalyst Preparations

Several classes of catalysts for the conversion of 2,3-butanediol tobutadiene were prepared for high-throughput screening. Representativeexamples of the preparations of these catalysts are described here.Other catalysts used in screening experiments were purchased or obtainedas free samples from commercial vendors.

Oxide by Nitrate Decomposition

Metal oxide catalysts were prepared by thermal decomposition of theirnitrate salts. The respective metal nitrate decomposition temperatures(Table 1) were found in the literature (Wendlandt, Analytica ChimicaActa, 15:435-439, 1956; Wendlandt, J. of Inorg. and Nuclear Chem.,12(3,4): 276-280, 1960; Haire, R. G. “The Thermal Decomposition ofBerkellium Compounds”, Link:http://www.osti.gov/bridge/purl.cover.jsp?purl=/44549027-yMjUrq/). Thepreparations of La and Nd oxides are described and are illustrative ofthe method used. The decomposition temperatures of La(NO₃)₃.6 H₂O andNd(NO₃)₃.6 H₂O were reported to be 780° C. and 830° C., respectively.Two grams of each of the above salts were placed in porcelain cruciblesand place in a muffle furnace. A low flow of air was admitted. Crucibleswere heated to 850° C. at 5° C./min, held for 2 h, and cooled to ambientat 10° C./min. The resulting oxides were ground to a fine powder(catalysts 5-6 and 5-7 in Example 2).

Metal nitrates were precursors for metal oxides deposited on varioussupports. In₂O₃ was supported on silica gel by impregnating indiumnitrate into Sigma Aldrich Grade 7754 Silica Gel (70-230 mesh). Theappropriate weight of indium nitrate to make a 10% In₂O₃ loaded silicawas dissolved in the previously determined impregnation volume. Theindium solution was added dropwise to the silica with vigorous mixing tomake a free-flowing powder. The powder was dried slowly in an oven withperiodic shaking to encourage uniform drying. The material was thencalcined in air at 500° C. (5° C./min heating rate) and held for 2hours. The cooled catalyst was light yellow.

10 wt % In₂O₃ on Hyperion CS-02C-063-XD was prepared by impregnationwith an aqueous indium nitrate solution. The impregnated material wastumbled to age the catalyst precursor, dried during tumbling under astream of hot air to remove most of the water, then further dried in avacuum oven at 75° C. The dried material was then washed with 28%ammonia to convert the indium to the insoluble hydroxide form. Thematerial was then dried in the vacuum oven at 75° C., then atatmospheric pressure at 115° C. This material was used for catalysttesting.

TABLE 1 Nitrate decomposition temperatures in rare-earth oxide syntheseNitrate Decomposition Rare-earth Oxide Temperature (° C.) La₂O₃ 850° C.Pr₆O₁₁ 550° C. Nd₂O₃ 850° C. Sm₂O₃ 750° C. Eu₂O₃ 800° C. Gd₂O₃ 800° C.Tb₄O₇ 450° C. Dy₂O₃ 800° C. Ho₂O₃ 650° C. Er₂O₃ 650° C. Tm₂O₃ 650° C.Yb₂O₃ 750° C. Lu₂O₃ 600° C. Y₂O₃ 500° C. Sc₂O₃ 550° C.

Oxide by Oxalate Decomposition

Metal oxide catalysts were prepared from their oxalate precursors, whichin turn were prepared from the nitrates by precipitation with oxalicacid. The preparation of In₂O₃ is illustrative. 14.08 g In(NO₃)₃.5 H₂Owas dissolved in 50 mL H₂O. 6.81 g oxalic acid was dissolved in 30 mLH₂O with gentle heating. Addition of the oxalic acid to the indiumnitrate solution resulted in the formation of a thick white gel, whichwas filtered and washed three times. The resulting solid was dried at120° C. for 2 h, then heated to 550° C. at 5° C./min, held for 4 h, thencooled to 30° C. at about 10° C./min. The solid was ground to a finepowder and recalcined at 550° C. for 2 h to give a dull yellow powder(catalyst 4-4 in Example 2).

Similarly, In₂O₃ can be prepared using ammonium oxalate in place ofoxalic acid. 16.90 g In(NO₃)₃.5 H₂O was dissolved in 50 mL H₂O. 9.21 gammonium oxalate was dissolved in 85 mL H₂O with gentle heating.Addition of the ammonium oxalate to the indium nitrate solution resultedin the formation of a thick white precipitate. The volume of the mixturewas reduced by gentle evaporation and the remaining slurry was placedinto an oven at 90° C. to dry overnight. The resulting solid was thenheated to 550° C. at 2° C./min, held for 6 h, then cooled to 25° C. atabout 3° C./min. The fluffy yellow solid was pelletized and sieved to a60-100 mesh fraction for catalyst testing (Table 37 in Example 5).

A portion of the In₂O₃ prepared by the ammonium oxalate preparation wasdoped with lithium ion. Sufficient lithium nitrate was dissolved inwater and slurried with a fraction of the In₂O₃. The slurry was thenslowly dried in an oven at 90° C., then heated to 600° C. at 3° C./h,and held for 4 h to calcine the material. The 60-100 mesh fraction wasused for catalyst testing.

Ga₂O₃ was prepared from the nitrate by precipitation with ammoniumoxalate, in the same manner as described above for In₂O₃. The 60-100mesh fraction was used for catalyst testing.

Oxide Deposited on Dried Hydrous Zirconia (Zr(OH)₄)

The preparation of 10% Sc₂O₃ on hydrous zirconia is illustrative of thisclass of catalysts. 10.00 g of water was added to 4.00 g of MELFZO1501/09 powder (MEL Chemicals) in a beaker. 1.8062 g Sc(NO₃)₃.5 H₂Owas dissolved in 10.00 mL H₂O and added to the zirconia slurry withstirring. After about 5 min, 5 mL 29% ammonia solution was added,resulting in coagulation to a gelatinous mass. The solids were filteredand washed several times with H₂O, then dried at 60° C. overnight. Thisuncalcined material was used as a catalyst in screening experiments(catalyst 2-3 in Example 2). In addition, a portion of the material wascalcined at 550° C. for 2 h and also screened for catalytic activity(catalyst 2-4 in Example 2).

Oxide Deposited on Calcined Zr(OH)₄

Hydrous zirconia powder (MEL FZO1501/06) was heated to 550° C. at 5°C./min, calcined at 550° C. for 4 h, then cooled to ambient. As arepresentative example of the general preparation used, 6.98 g of thismaterial was slurried with 100 mL H₂O. Tm(NO₃)₃.5 H₂O (1.79 g) wasdissolved in H₂O (30 mL) and added to the zirconia slurry with stirring.29% ammonia solution (10 mL) was then added to form a gel, which wasfiltered and washed several times. The filter cake was dried under housevacuum at 80° C. overnight, then calcined with a flow of air at 550° C.for 2 h (catalyst 1-6 in Example 2).

Calcium-Doped Oxide Via Oxalate Decomposition

As one example, 11.79 g Lu(NO₃)₃.x H₂O and 0.40 g Ca(NO₃)₂.4 H₂O weredissolved in 100 mL H₂O. 4.97 g of oxalic acid was dissolved in 50 mLwarm H₂O and added to the Lu/Ca solution to form a gel. Solids werefiltered and washed several times with H₂O and dried at 80° C. underhouse vacuum overnight. The solid product was then calcined at 550° C.for 6 h in flowing air (catalyst 4-6 in Example 2).

Other Oxide Preparations

Hafnium oxide, HfO₂, was prepared by precipitating the hydrous oxidefrom a solution of hafnium chloride using an aqueous ammonia solution.The precipitate was washed, dried, and calcined at 600° C. prior to use.

A 50% ZnO/50% SiO₂ catalyst was prepared by mixing a zinc nitratesolution with a silica sol, drying the mixture, and calcining theresulting solids at 600° C. for 2 hours.

An Al_(0.75)Zn_(0.25)O_(x) catalyst composition was prepared that hadpreviously been reported (Bhattacharyya, Ind. Eng. Chem. Process Des.Dev., 2(1), 45-51, 1963). The method used to prepare the catalyst was aco-precipitation procedure. A first solution containing dissolvedammonium carbonate was added to a second solution containing dissolvedaluminum nitrate and zinc nitrate. The resulting precipitate wasdeionized water washed, then dried and calcined at 600° C. for 2 hours.

Phosphate Catalyst Preparation

Phosphate catalysts were synthesized by a method typified by thesynthesis of barium phosphate described here. 10.19 g of diammoniumhydrogen phosphate [(NH₄)₂HPO₄], 29 mL of 29% aqueous ammonia [NH₃], and100 mL of deionized (DI) water were combined. The contents were gentlyheated and stirred to completely dissolve the solids. 28.97 g of bariumacetate [Ba(C₂H₃O₂)₂] and 10 mL of DI water were added together andmixed well at room temperature for several minutes until the solids weredissolved. The Ba(C₂H₃O₂)₂ solution was added drop wise to the(NH₄)₂HPO₄ solution while stirring continuously. After all the solutionwas added, stirring was ceased and the fine-grain white precipitate thatformed was settled out. After allowing the solids to settle for ˜20minutes, the supernatant solution (nearly water white) was drawn offwithout disturbing the settled solids. Then, 200 mL of fresh DI waterwas added to the beaker to wash the solids and stirred vigorously for afew minutes. The re-slurried solids were allowed to settle for ˜20minutes and the clear solution above the settled solids was drawn off.The washing procedure was repeated one more time. Then, the twice-washedslurry was vacuum filtered using a Millipore® 0.45 μm filter. The filtercake was additionally washed on the filter with ˜250 mL of fresh DIwater. After washing, the filter cake was allowed to air dry on thefilter for ˜1 hour, and then the filter assembly and the cake wereplaced in a vacuum oven overnight at 120° C. The dried cake was removedfrom the vacuum oven and recovered from the filter. The soft powderchunks were ground gently in a mortar and pestle for uniformity(catalyst 4-13 in Example 2).

Commercial Catalysts

Commercial catalysts were obtained from MEL Chemicals, Degussa (Evonik),Praxair, Coorstech, Alfa-Aesar, Engelhard, Tosoh, Unitec Ceramics,Teledyne Wah Chang, and Cerac as indicated in Table 3.

Example 1 Pyroprobe Evaluation of Catalysts

The feedstock was 10 wt % BDO (Aldrich) in deionized (DI) water. Thecatalyst (˜2 mg of powder) was loaded into a quartz tube (25 mm long×1.9mm I.D.; open at both ends), and held in position using a quartz woolplug on both ends of the powder layer. Approximately 1 μL of feedsolution was subsequently dispensed onto the back quartz wool plug thenloaded into the pyroprobe wand with the liquid-containing end down, sothat upon heating the liquid feed vapors would be carried through thecatalyst bed. After the tube was loaded into the pyroprobe wand, the endof the wand was inserted into the pyroprobe unit and sealed. Heliumcarrier gas flowed through the probe wand and over the quartz wool plugsand catalyst. Upon initiation of the unit, a heating coil encircling thequartz tube, rapidly heated the tube and its contents to ˜600° C. andmaintained it at that temperature for usually 15 seconds. Carrier gasflows were typically 20 cc/m of He through the pyroprobe. Reactant andproduct vapors were rapidly carried out of the quartz tube and adsorbedonto a Carbopack bed at 40° C., then later desorbed from the adsorbentbed at 300° C. The desorbed products were carried into the GC/MS unitfor separation and analysis. Area percent reports were generated forpercent conversion of BDO and product selectivity to 1,3 butadiene,methyl vinyl carbinol, MEK, and isobutyraldehyde (IBA). Aldrich BDO wasa mixture of d/l and meso isomers. Early analyses integrated over bothisomers (reported as BDO) until method improvements allowed separatequantification.

Conversion and product selectivity data were based on GC/MS areapercents for BDO feedstock and other products produced. A ranking of thenine best pyroprobe test results are shown in Table 2. A completelisting of results obtained from all of the catalysts tested ispresented in Table 3. Catalysts that produced 1,3BD and/or MVC wereconsidered, since MVC is relatively easily converted to 1,3BD. Thecatalyst designation, the optimum test temperature used, and thecombined 1,3BD+MVC yield for that condition are given for each of thenine best catalyst/conditions tested. Optimal temperatures in thepyroprobe are not necessarily the optimal temperatures in other reactordesigns.

TABLE 2 Best results for 1,3BD and MVC production in pyroprobe testingCatalyst Optimal T, ° C. 1,3BD + MVC % Yield MEL ALZ22¹ 500 61.4 MELXZO691-01² 500 58.0 Tm₂O³ 500 56.3 MEL ALZ22¹ 500 56.0 MEL FZO2089³ 50053.8 MEL ALZ5C-4/D⁴ 500 48.7 MEL ALZ22¹ 500 42.7 MEL FZO922⁵ 500 33.9Sc₂O₃ 700 31.7 ¹A mixed oxide of Al, La, and Zr, obtained from MELChemicals, Inc. ²Zr(OH)₄—Ca(OH)₂, obtained from MEL Chemicals, Inc. ³Amixed oxide of Al, La, and Zr (equivalent to ALZ22), obtained from MELChemicals, Inc. ⁴A mixed oxide of Al and Zr, obtained from MEL Chemicals⁵Zr(OH)₄(or ZrO₂•2H₂O), obtained from MEL Chemicals

As shown in Table 2, mixed oxides including Al, La, and Zr performedwell. Oxides of Al/Zr, Zr/Ca, Tm, and Sc also gave good results.

TABLE 3 Summary of pyroprobe runs for the conversion of BDO to 1,3BD BDO1,3BD 1,3BD MVC MVC MEK MEK Other Other % % % % % % % % % Run CatalystDescriptor Notes T (° C.) Conv. Sel. Yield Sel. Yield Sel. Yield Sel.Yield 1 Silica Gel Degussa 300 10.0 0 0 0 0 0 0 100.0 10.0 Aerosil 380 2Silica Gel Degussa 500 93.0 8.6 8.0 0 0 91.4 85.0 0 0 Aerosil 380 3Alpha Alumina Coorstech 300 10.0 0 0 0 0 0 0 100.0 10.0 2886-50-1 4Alpha Alumina Coorstech 500 95.0 8.4 8.0 0 0 91.6 87.0 0 0 2886-50-1 5Pr-doped CeO_(x) 300 5.0 0 0 0 0 0 0 100.0 5.0 (deoxygenated) 6 Pr-dopedCeO_(x) 500 5.0 0 0 0 0 0 0 100.0 5.0 (deoxygenated) 7 Pr-doped CeO_(x)700 5.0 0 0 0 0 0 0 100.0 5.0 (deoxygenated) 8 CeO₂ Alfa-Aesar  99.9%300 5.0 0 0 0 0 0 0 100.0 5.0 9 CeO₂ Alfa-Aesar  99.9% 500 50.0 0 0 0 080.0 40.0 20.0 10.0 10 WO_(2.97) Alfa-Aesar 99.99% 300 65.0 0 0 0 0 76.950.0 23.1 15.0 11 WO_(2.97) Alfa-Aesar 99.99% 500 5.0 0 0 0 0 0 0 100.05.0 12 La₂O₃ Alfa-Aesar 99.99% 300 5.0 0 0 0 0 0 0 100.0 5.0 13 La₂O₃Alfa-Aesar 99.99% 500 5.0 0 0 0 0 0 0 100.0 5.0 14 3 mole % Y-Stab. ZrO₂Degussa VP 300 5.0 0 0 0 0 0 0 100.0 5.0 3-YSZ (40) 15 3 mole % Y-Stab.ZrO₂ Degussa VP 500 75.5 23.3 17.6 16.7 12.6 60.1 45.4 −0.1 −0.1 3-YSZ(40) 16 La + Al Doped ZrO₂ MEL ALZ22 300 10.0 0 0 0 0 0 0 100.0 10.0 17La + Al Doped ZrO₂ MEL ALZ22 500 99.4 43.0 42.7 0 0 45.8 45.5 11.3 11.218 La + Al Doped ZrO₂ MEL ALZ22 (1st Repeat) 500 90.0 0 0 0 0 100.0 90.00 0 19 La + Al Doped ZrO₂ MEL ALZ22 (2nd Repeat) 500 90.0 16.4 14.8 0 066.7 60.0 16.9 15.2 20 Quartz Wool 79.0 9.2 7.3 0 0 62.2 49.1 28.6 22.621 La + Al Doped ZrO₂ MEL ALZ22 (Fresh Cat.) 500 75.0 33.3 25.0 0 0 48.736.5 18.0 13.5 22 La + Al Doped ZrO₂ MEL ALZ22 (1st Repeat) 500 93.565.7 61.4 0 0 26.5 24.8 7.8 7.3 23 La + Al Doped ZrO₂ MEL ALZ22 (2ndRepeat) 500 94.0 56.5 53.1 0 0 27.8 26.1 15.7 14.8 24 La + Al Doped ZrO₂MEL ALZ22 (3rd Repeat) 500 50.0 41.0 20.5 0 0 46.2 23.1 12.8 6.4 25 La +Al Doped ZrO₂ MEL ALZ22 (4th Repeat) 500 92.0 50.4 46.4 0 0 37.3 34.312.3 11.3 26 La + Al Doped ZrO₂ MEL ALZ22 (5th Repeat; 500 93.3 63.259.0 0 0 30.0 28.0 6.8 6.3 N₂ flow 60% of that in Run 25) 27 La + AlDoped ZrO₂ MEL ALZ22 (6th Repeat; 500 53.0 64.9 34.4 0 0 65.1 34.5 −30.0−15.9 N₂ flow 40% of that in Run 25) 28 3 mole % Y-Stab. ZrO₂ Degussa VP500 38.0 21.1 8.0 10.8 4.1 41.6 15.8 26.6 10.1 3-YSZ (40) 29 3 mole %Y-Stab. ZrO₂ Degussa VP 500 38.0 23.7 9.0 14.5 5.5 42.9 16.3 18.9 7.23-YSZ (40) 30 5% Phosphomolybdic acid Engelhard 250 53.0 0 0 0 0 64.234.0 35.8 19.0 (PMA) on TiO₂ 0720 31 5% PMA on TiO₂ 0720 Engelhard 35050.0 0 0 0 0 58.0 29.0 42.0 21.0 32 Sm₂O₃ 300 61.5 0 0 0 0 65.0 40.035.0 21.5 33 Sm₂O₃ 500 55.0 9.6 5.3 0 0 75.1 41.3 15.3 8.4 34 Sm₂O₃ 70074.5 19.7 14.7 0 0 53.7 40.0 26.6 19.8 35 Yb₂O₃ 500 65.0 20.8 13.5 0 038.5 25.0 40.8 26.5 36 Yb₂O₃ 700 60.0 2.7 1.6 0 0 59.7 35.8 37.7 22.6 37Gd₂O₃ 500 46.0 0 0 0 0 45.7 21.0 54.3 25.0 38 Ho₂O₃ 500 45.7 14.7 6.7 00 58.0 26.5 27.4 12.5 39 Ho₂O₃ 700 57.5 7.9 4.6 0 0 56.7 32.6 35.4 20.340 Eu₂O₃ 500 30.0 6.7 2.0 0 0 60.0 18.0 33.3 10.0 41 Eu₂O₃ 700 66.0 14.59.6 5.0 3.3 50.0 33.0 30.5 20.1 42 Dy₂O₃ 500 49.0 0 0 0 0 61.2 30.0 38.819.0 43 Dy₂O₃ 700 63.4 8.2 5.2 0 0 63.1 40.0 28.7 18.2 44Zr(OH)₄—Ca(OH)₂ MEL XZO 300 44.0 0 0 0 0 54.5 24.0 45.5 20.0 691-01 45Zr(OH)₄—Ca(OH)₂ MEL XZO 500 97.5 59.5 58.0 0 0 24.6 24.0 15.9 15.5691-01 46 Zr(OH)₄—Ca(OH)₂ MEL XZO 700 84.0 28.5 23.9 0 0 38.1 32.0 33.528.1 691-01 47 Zr(OH)₄—Ca(OH)₂ MEL XZO (1st Repeat) 500 96.4 44.6 43.0 00 27.0 26.0 28.4 27.4 691-01 48 Zr(OH)₄—Ca(OH)₂ MEL XZO (2nd Repeat) 50066.4 30.1 20.0 0 0 39.2 26.0 30.7 20.4 691-01 49 Zr(OH)₄—Ca(OH)₂ MEL XZO(3rd Repeat) 500 55.0 6.4 3.5 0 0 61.8 34.0 31.8 17.5 691-01 50 CalcinedZr(OH)₄—Ca(OH)₂ MEL XZO 500 73.3 27.3 20.0 7.5 5.5 47.7 35.0 17.5 12.8(900 C.) 691-01 51 Calcined Zr(OH)₄—Ca(OH)₂ MEL XZO (1st Repeat) 50049.9 21.4 10.7 0 0 49.1 24.5 29.5 14.7 (900 C.) 691-01 52 Al-Doped ZrO₂MEL 500 100.0 48.7 48.7 0 0 28.6 28.6 22.7 22.7 ALZ5C-4/D 53 Al-DopedZrO₂ MEL 500 74.0 34.7 25.7 0 0 33.8 25.0 31.5 23.3 ALZ5C-4/D 54 Zr(OH)₄MEL 500 100.0 33.9 33.9 0 0 20.0 20.0 46.1 46.1 FZ0922 55 Zr(OH)₄ MEL700 83.5 35.9 30.0 0 0 49.1 41.0 15.0 12.5 FZ0922 56 Ce-Doped ZrO₂ MEL802 500 50.4 26.8 13.5 0 0 48.2 24.3 25.0 12.6 57 Ce-Doped ZrO₂ MEL 802700 88.0 13.3 11.7 0 0 46.6 41.0 40.1 35.3 58 Calcined La + Al DopedZrO₂ MEL ALZ22 500 69.0 25.4 17.5 0 0 46.8 32.3 27.8 19.2 (900 C.) 59Calcined La + Al Doped ZrO₂ MEL ALZ22 (1st Repeat) 500 53.0 28.7 15.2 00 47.2 25.0 24.2 12.8 (900 C.) 60 Calcined La + Al Doped ZrO₂ MEL ALZ22(2nd Repeat) 500 63.0 21.7 13.7 0 0 50.0 31.5 28.3 17.8 (900 C.) 61 8mole % Y-Stab. ZrO₂ Tosoh 300 0 0 0 0 0 0 0 0 0 TZ-8YS 62 8 mole %Y-Stab. ZrO₂ Tosoh 500 38.0 0 0 0 0 56.8 21.6 43.2 16.4 TZ-8YS 63 10mole % Y-Stab. ZrO₂ Tosoh 300 0 0 0 0 0 0 0 0 0 TZ-10YS 64 10 mole %Y-Stab. ZrO₂ Tosoh 500 28.0 10.0 2.8 0 0 50.7 14.2 39.3 11.0 TZ-10YS 6513 mole % Y-Stab. ZrO₂ Unitec 300 0 0 0 0 0 0 0 0 0 Ceramics 66 13 mole% Y-Stab. ZrO₂ Unitec 500 38.0 0 0 0 0 16.6 6.3 83.4 31.7 Ceramics 67La + Al Doped ZrO₂ MEL ALZ22 500 88.0 63.6 56.0 31.0 27.3 0 0 5.3 4.7 68Ho₂O₃ 300 11.0 0 0 0 0 0 0 100.0 11.0 69 Ho₂O₃ 500 7.0 0 0 0 0 0 0 100.07.0 70 Ho₂O₃ 700 40.0 0 0 0 0 60.8 24.3 39.3 15.7 71 Y₂O₃ 300 0 0 0 0 00 0 0 0 72 Y₂O₃ 500 0 0 0 0 0 0 0 0 0 73 3 mole % Y-Stab. ZrO₂ DegussaVP 500 38.0 23.7 9.0 14.5 5.5 42.9 16.3 18.9 7.2 3-YSZ (40) 74 3 mole %Y-Stab. ZrO₂ Degussa VP 500 37.1 21.0 7.8 11.1 4.1 42.6 15.8 25.3 9.43-YSZ (40) 75 Y₂O₃ 300 1.0 0 0 0 0 0 0 100.0 1.0 76 Y₂O₃ 500 6.0 0 0 0 00 0 100.0 6.0 77 La₂O₃ 500 8.0 0 0 0 0 0 0 100.0 8.0 78 La₂O₃ 700 23.2 00 0 0 53.0 12.3 47.0 10.9 79 Nd₂O₃ 500 5.0 0 0 0 0 0 0 100.0 5.0 80Nd₂O₃ 700 33.0 20.6 6.8 10.3 3.4 48.5 16.0 20.6 6.8 81 Ho₂O₃ 500 6.0 0 00 0 0 0 100.0 6.0 82 Ho₂O₃ 700 40.0 0 0 0 0 78.3 31.3 21.8 8.7 83 Er₂O₃300 1.0 0 0 0 0 0 0 100.0 1.0 84 Er₂O₃ 500 13.0 30.8 4.0 0 0 31.5 4.137.7 4.9 85 Er₂O₃ 700 42.0 22.1 9.3 5.7 2.4 61.4 25.8 10.7 4.5 86 Tm₂O₃300 1.0 0 0 0 0 0 0 100.0 1.0 87 Tm₂O₃ 500 91.5 61.5 56.3 0 0 26.3 24.112.1 11.1 88 Tm₂O₃ 700 89.0 28.2 25.1 0 0 28.5 25.4 43.3 38.5 89 Tb₄O₇300 30.0 0 0 0 0 0 0 100.0 30.0 90 Tb₄O₇ 500 48.0 0 0 0 0 18.1 8.7 81.90 91 Tb₄O₇ 700 64.0 0 0 0 0 20.5 13.1 79.5 50.9 92 Lu₂O₃ 300 4.0 0 0 0 00 0 100.0 4.0 93 Lu₂O₃ 500 32.5 30.8 10.0 0 0 36.9 12.0 32.3 10.5 94Lu₂O₃ 700 85.7 20.1 17.2 6.2 5.3 22.2 19.0 51.6 44.2 95 Sc₂O₃ 300 7.0 00 0 0 71.4 5.0 28.6 2.0 96 Sc₂O₃ 500 45.4 30.2 13.7 11.2 5.1 33.0 15.025.6 11.6 97 Sc₂O₃ 700 75.3 29.2 22.0 12.9 9.7 27.0 20.3 30.9 23.3 98HfO₂ 300 4.0 0 0 0 0 0 0 100.0 4.0 99 HfO₂ 500 31.5 27.6 8.7 0 0 38.712.2 33.7 10.6 100 HfO₂ 700 40.0 0 0 0 0 78.3 31.3 21.8 8.7 101 Pr₆O₁₁300 4.0 0 0 0 0 0 0 100.0 4.0 102 Pr₆O₁₁ 500 73.0 0 0 0 0 11.0 8.0 89.065.0 103 Pr₆O₁₁ 700 68.0 0 0 0 0 17.1 11.6 82.9 56.4 104 50 mole % ZnO/500 23.9 11.3 2.7 0 0 68.2 16.3 20.5 4.9 50 mole % SiO₂ 105 50 mole %ZnO/ 700 40.5 15.3 6.2 0 0 60 24.3 24.7 10.0 50 mole % SiO₂ 106 HighPurity HfO₂ powder Teledyne 99.99% 500 24.7 12.2 3.0 5.3 1.3 80.0 14.822.6 5.6 Wah Chang HfO₂ 107 High Purity HfO₂ powder Teledyne 99.99% 70067.5 9.8 6.6 4.7 3.2 60.0 40.5 25.5 17.2 Wah Chang HfO₂ 108 3 mole % ScStabilised ZrO₂ Praxair 500 14.7 10.2 1.5 3.4 0.5 58.6 8.6 27.8 4.1 1093 mole % Sc Stabilised ZrO₂ Praxair 700 68.5 14.6 10.0 1.9 1.3 57.2 39.226.3 18.0 110 10 wt % Tm₂O₃ on Aerosil 380 500 65.8 11.6 7.6 0 0 62.641.2 25.8 17.0 111 10 wt % Tm₂O₃ on Aerosil 380 700 79.4 13.4 10.6 0 061.5 48.8 25.2 20.0 112 Ta₂O₅ -325 mesh powder Cerac 500 17.8 10.1 0 0 058.4 0 31.5 5.6 T-1013 113 La + Al Doped ZrO₂ MEL ALZ22 500 94.8 57.054.0 0 0 32.1 30.4 11.0 10.4 114 La + Al Doped ZrO₂ MEL ALZ22 700 100.00 0 0 0 0 0 100.0 100.0 115 La + Al Doped ZrO₂ MEL MEL ALZ22 500 84.056.0 47.0 0 0 30.4 25.5 13.7 11.5 FZO2089 Equivalent 116 La + Al DopedZrO₂ MEL MEL ALZ22 700 89.8 24.5 22.0 0 0 55.7 50.0 19.8 17.8 FZO2089Equivalent 117 Calcined La + Al Doped ZrO₂ MEL 500 92.5 51.9 48.0 0 025.4 23.5 22.7 21.0 (550 C.) FZO2089 118 Calcined La + Al Doped ZrO₂ MEL700 87.1 47.1 41.0 0 0 36.2 31.5 16.8 14.6 (550 C.) FZO2089 119 CalcinedLa + Al Doped ZrO₂ MEL 500 92.9 57.9 53.8 0 0 23.1 21.5 18.9 17.6 (650C.) FZO2089 120 Calcined La + Al Doped ZrO₂ MEL 700 87.4 47.3 41.3 0 034.3 30.0 18.4 16.1 (650 C.) FZO2089 121 Boron Oxide Glass 500 56.9 5.33.0 0 0 101.9 58.0 −7.2 −4.1

Example 2 High Throughput Catalyst Testing

Catalysts for high throughput testing were either commercially availablecatalysts, commercially available catalysts that had been modified, orcatalysts prepared in-house. Catalysts (50 mg) were loaded into taperedreactor tubes, with an OD of 3 mm, ID of 2.6 mm, and length of 300 mm.When loading the reactors, a small portion of Zirblast® (ceramic beadscomprising 68-70% ZrO₂, 28-33% SiO₂, and <10% Al₂O₃, with a crystalstructure of 68% zirconia and 32% vitreous phase, specific gravity 3.85g/cm³, bulk density 2.3 kg/L, Saint-Gobain, France) was added to thebottom of each reactor. Pre-weighed portions of the catalyst were addedto each tube. The remaining volume of the tube was filled with Zirblast®and plugged with quartz wool.

The catalysts were activated by heating at 10° C./min to a temperatureof 425° C. with a 12.5 mL/min He flow rate at ambient pressure, After a2-hour hold, each reactor block was cooled to the target reactiontemperature. The He flow was reduced to 1 mL/min and flow of neat BDOwas then started at 0.01 mL/min. The liquid collection autosampler wascooled to 4° C. After a 10 minute wait at the reaction conditions,collection of sample set #1 began. For liquid collection, the outletgases were bubbled through a trapping solvent of dimethyl diglymecontaining an internal standard of about 0.5% 1-octanol (3 mL per vial).Liquid sampling for this and each subsequent condition was done over a 3hour period. On-line gas GC analysis was performed at the beginning andend of the sampling time. Upon completion of liquid sampling at thefirst condition, the sample vial was replaced, the reactor conditionswere changed, and sample set #2 was started in the same manner followinga 10 min wait period. All liquid samples were weighed after the run.Samples were diluted and run on a GC-FID.

Table 4 shows the catalysts present in each run. Tables 5-34 show thescreening results.

TABLE 4 Screening 1 1 1-1 La₂O₃/Al₂O₃/ZrO₂ MEL Chemicals, Inc. (MEL)FZO2089 2 1-2 Tm₂O₃ oxide via nitrate decomposition 3 1-3 Tm₂O₃ oxidevia oxalate decomposition 4 1-4 Tm₂O₃ oxide on Zr(OH)₄ support - dried 51-5 Tm₂O₃ oxide on Zr(OH)₄ support - calcined 6 1-6 Tm₂O₃ oxide oncalcined Zr(OH)₄ support - recalcined 7 1-7 La₂O₃/ZrO₂ MEL XZO945-03 10%La-doped ZrO₂, calcined 600° C. 8 1-8 Ca-doped ZrO₂ MEL XZ0691-01.calcined 900° C. Screening 2 1 2-1 SC₂O₃ oxide via nitrate decomp 2 2-2La₂O₃/Al₂O₃/ZrO₂ MEL FZO2089 3 2-3 SC₂O₃ oxide on Zr(OH)₄ support -dried 4 2-4 SC₂O₃ oxide on Zr(OH)₄ support - calcined 5 2-5 Dy₂O₃ oxidevia nitrate decomp 6 2-6 ZrO₂ MEL XZO1501-06 as received 7 2-7 ZrO₂ MELXZO1501-09 as received 8 2-8 ZrO₂ MEL XZO1501-06 calcined Screening 3 13-1 La₂O₃/Zr₂O₃ MEL XZO945-03 10% La-doped ZrO₂, calcined 600 C. 2 3-2Er₂O₃ oxide on Zr(OH)₄ support - dried 3 3-3 Er₂O₃ oxide on Zr(OH)4support - calcined 4 3-4 La₂O₃ oxide on Zr(OH)₄ support - dried 5 3-5La₂O₃ oxide on Zr(OH)₄ support - calcined 6 3-6 Lu₂O₃ oxide on Zr(OH)₄support - dried 7 3-7 Lu₂O₃ oxide on Zr(OH)₄ support - calcined 8 3-9ZnO oxide on Zr(OH)₄ support - calcined Screening 4 and Screening 4Repeat 1 4-1 La₂O₃/Zr₂O₃ XZO945-03 10% La-doped ZrO₂, calcined 600 C. 24-2 ZrO₂ oxide on Zr(OH)₄ support - dried 3 4-3 ZrO₂ oxide on Zr(OH)₄support - calcined 4 4-4 In₂O₃ oxide via oxalate decomposition, oxalicacid preparation 5 4-5 In₂O₃ oxide on Zr(OH)₄ support - calcined 6 4-6Lu₂O₃ Ca-doped oxide via oxalate 7 4-7 Lu₂O₃ oxide via nitratedecomposition 8 4-8 Er₂O₃ oxide on calcined Zr(OH)₄ support - recalcined9 4-9 Er₂O₃ oxide on calcined Zr(OH)₄ support - recalcined 10 4-10 Y₂O₃oxide via oxalate decomposition 11 4-11 Y₂O₃ oxide via nitratedecomposition 12 4-12 Y₂O₃ Ca-doped oxide via oxalate 13 4-13 Ba₃(PO₄)₂phosphate co-ppt, dried 14 4-14 LiCaPO₄ phosphate co-ppt, dried 15 4-15BPO₄ phosphate co-ppt, calcined 16 4-16 Mg₃(PO₄)₂ phosphate co-ppt,calcined Screening 5 1 5-1 La₂O₃/ZrO₂ MEL XZO945-03 10% La-doped ZrO₂,calcined 600° C. 2 5-2 Er₂O₃ oxide via nitrate decomposition 3 5-3 Er₂O₃oxide via nitrate decomposition 4 5-4 Gd₂O oxide via nitratedecomposition 5 5-5 HO₂O₃ oxide via nitrate decomposition 6 5-6 La₂O₃oxide via nitrate decomposition 7 5-7 Nd₂O₃ oxide via nitratedecomposition 8 5-8 Pr_(e)O₁₁ oxide via nitrate decomposition 9 5-9Sm₂O₃ oxide via nitrate decomposition 10 5-10 Tb₄O₇ oxide via nitratedecomposition 11 5-11 Yb₂O₃ oxide via nitrate decomposition 12 5-12MgAl₂O₄ oxide via nitrate decomposition 13 5-13 Ca-doped CeO₂ oxide vianitrate decomposition 14 5-14 MoOHD 3 oxide via AFIM decomposition 155-15 HfO2 oxide via hydroxide decomposition 16 5-16 CeO₂/ZrO₂ MEL 802Screening 6 1 6-1 La₂O₃/ZrO₂ MEL XZO945-03 10% La-doped ZrO₂, calcined600 C. 2 6-2 Al/ZrO₂ MEL ALZ5C-4/D 3 6-3 Ca/ZrO₂ MEL XZO691-01 4 6-4WO₃/ZrO₂ MEL XZO1251-01 5 6-5 CeO₂/La₂O₃/ZrO₂ MEL XZO892-02 6 6-6SiO₂/ZrO₂ MEL XZO645-01 7 6-7 CeO₂/La₂O₃/ZrO₂ MEL XZO1291-01 (highporosity) 8 6-8 La₂O₃/ZrO₂ MEL XZO945-3 9 6-9 La₂O₃/ZrO₂ 900° C.calcined 10 6-10 Zr(OH)₄ MEL XZO922 11 6-11 In₂O₃ 900° C. calcined(In₂O₃from oxalic acid preparation) 12 6-12 Er₂O₃ 900° C. calcined 136-13 Yb₂O₃ 900° C. calcined 14 6-14 Tm/ZrO₂ 900° C. calcined 15 6-15Lu₂O₃/ZrO₂ 900° C. calcined 16 6-16 SC₂O₃/ZrO₂ 900° C. calcinedScreening 7 - (MVC to BD) 1 7-1 Ba₃(PO₄)₂ 2 7-2 LiCaPO₄ 3 — — (no flowduring expt) 4 7-4 Mg₃(PO₄)₂ 5 — — (no flow during expt) 6 — — (no flowduring expt) 7 7-7 ZSM-5 (30) 8 7-8 beta zeolite 9 — — (no flow duringexpt) 10 — — (no flow during expt) 11 7-11 Grace Davicat ® SIAL 3111silica-alumina(13% Al₂O₃), 475 m²/g, 1.1 mL/g, 74 μm average pore size12 7-12 Grace Davicat ® SIAL 3113 silica-alumina (13% Al₂O₃), 573 m²/g,0.76 mL/g, 73 μm average pore size 13 7-13 Grace Davicat ® SIAL 3115silica-alumina (13% Al₂O₃), 360 m2/g, 1.2 mL/g, 68 μm average pore size14 7-14 Grace Davicat ® SIAL 3125 silica-alumina (25% Al₂O₃), 552 m²/g,0.79 mL/g, 78 μm average pore size 15 7-15 Al₂O3 Engelhard 4126 16 7-16Al₂O3 Grace AL2200 Alumina

TABLE 5 Screening 1, 300° C., 3 h Catalyst: 1-1 1-2 1-3 1-4 1-5 1-6 1-71-8 BDO Conversion 68.0% 34.2% 19.5% 24.1% 15.4% 12.5% 18.4% — 1,3butadiene 0.1% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% butenes 0.0% 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.0% 4-vinyl-1- 0.2% 0.0% 0.2% 0.2% 0.2% 0.2% 0.2%0.2% cyclohexene acetone 0.3% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%isobutyraldehyde 1.3% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 2,3-butanedione0.7% 0.1% 0.1% 0.4% 0.3% 0.2% 0.5% 0.2% MEK 23.6% 0.5% 0.1% 1.7% 1.3%0.6% 1.0% 0.7% acetoin 3.1% 0.4% 0.3% 1.4% 0.8% 0.7% 0.9% 0.0% MVC 5.9%0.0% 0.0% 3.0% 1.4% 1.3% 1.5% 0.0% isobutanol 2.5% 0.1% 0.1% 1.2% 0.5%0.3% 0.5% 0.0% Total 37.7% 1.2% 0.9% 7.9% 4.5% 3.3% 4.6% 1.1%

TABLE 6 Screening 1 (cont'd), 300° C., 6 h Catalyst: 1-1 1-2 1-3 1-4 1-51-6 1-7 1-8 BDO Conversion 64.0% 22.9% 10.1% 8.7% 8.1% 2.3% 4.4% — 1,3butadiene 0.1% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% butenes 0.0% 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.0% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% cyclohexene acetone 1.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%isobutyraldehyde 1.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 2,3-butanedione0.6% 0.1% 0.1% 0.3% 0.3% 0.2% 0.3% 0.1% MEK 17.9% 0.3% 0.5% 1.5% 1.1%0.6% 0.8% 0.6% acetoin 2.5% 0.4% 0.3% 1.6% 0.7% 0.8% 0.7% 0.0% MVC 4.6%0.0% 0.0% 3.0% 1.3% 1.4% 1.1% 0.0% isobutanol 1.8% 0.0% 0.0% 1.2% 0.5%0.3% 0.4% 0.0% Total 29.5% 0.9% 0.9% 7.6% 3.9% 3.2% 3.2% 0.7%

TABLE 7 Screening 1 (cont'd), 350° C., 3 h Catalyst: 1-1 1-2 1-3 1-4 1-51-6 1-7 1-8 BDO Conversion 100.0% 36.2% 41.8% 89.1% 71.6% 59.3% 66.6%15.1% 1,3 butadiene 0.7% 0.1% 0.0% 0.1% 0.1% 0.1% 0.1% 0.1% butenes 0.1%0.1% 0.1% 0.2% 0.1% 0.2% 0.1% 0.1% 4-vinyl-1- 0.2% 0.3% 0.2% 0.5% 0.3%0.3% 0.3% 0.2% cyclohexene acetone 2.2% 0.3% 0.2% 2.2% 0.9% 0.8% 1.1%0.9% isobutyraldehyde 2.2% 0.3% 0.2% 2.2% 0.9% 0.8% 1.1% 0.9%2,3-butanedione 0.7% 1.0% 0.7% 2.1% 1.5% 1.4% 2.0% 1.0% MEK 28.4% 4.7%5.0% 21.0% 11.5% 7.8% 10.3% 5.3% acetoin 3.3% 3.7% 2.3% 0.1% 0.1% 0.1%9.7% 0.3% MVC 0.8% 1.6% 0.6% 3.6% 10.7% 0.5% 9.9% 0.6% isobutanol 5.0%1.4% 1.2% 15.3% 7.3% 5.1% 7.4% 0.1% Total 43.6% 13.2% 10.6% 47.2% 33.3%16.9% 42.2% 9.5%

TABLE 8 Screening 1 (cont'd), 350° C., 6 h Catalyst: 1-1 1-2 1-3 1-4 1-51-6 1-7 1-8 BDO Conversion 96.4% 21.2% 26.6% 82.5% 62.7% 60.6% 55.4%3.6% 1,3 butadiene 0.4% 0.0% 0.0% 0.1% 0.1% 0.1% 0.1% 0.0% butenes 0.1%0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 4-vinyl-1- 0.1% 0.0% 0.0% 0.3% 0.0%0.0% 0.0% 0.0% cyclohexene acetone 1.6% 0.0% 0.2% 2.2% 1.1% 0.6% 0.8%0.7% isobutyraldehyde 1.6% 0.0% 0.2% 2.2% 1.1% 0.6% 0.8% 0.7%2,3-butanedione 0.6% 0.9% 0.9% 2.1% 1.7% 1.3% 1.9% 0.8% MEK 22.2% 3.5%4.4% 19.5% 11.8% 6.4% 8.0% 3.8% acetoin 4.3% 3.2% 2.3% 0.1% 0.1% 8.4%8.7% 0.3% MVC 4.6% 1.6% 0.7% 19.0% 14.3% 13.1% 9.4% 0.5% isobutanol 4.9%1.1% 1.1% 15.8% 8.9% 4.5% 6.2% 0.0% Total 40.3% 10.3% 9.8% 61.3% 39.1%35.1% 36.0% 7.0%

TABLE 9 Screening 2, 300° C., 3 h Catalyst: 2-1 2-2 2-3 2-4 2-5 2-6 2-72-8 BDO Conversion 100.0% 84.4% 100.0% 100.0% 100.0% 100.0% 100.0%100.0% 1,3 butadiene 0.0% 0.1% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% butenes0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 4-vinyl-1- 0.0% 0.2% 2.2% 2.4%2.3% 2.2% 2.6% 2.1% cyclohexene acetone 2.3% 0.7% 0.0% 0.0% 0.0% 0.2%0.2% 0.0% isobutyraldehyde 0.0% 0.7% 0.0% 0.0% 0.0% 0.2% 0.2% 0.0%2,3-butanedione 0.2% 0.3% 0.3% 0.3% 0.3% 0.3% 0.4% 0.3% MEK 0.8% 22.2%1.6% 1.5% 1.1% 1.8% 2.6% 1.2% acetoin 0.5% 2.3% 1.6% 1.1% 0.4% 1.6% 2.3%0.9% MVC 3.5% 3.8% 2.2% 1.8% 0.0% 4.0% 5.1% 2.1% isobutanol 0.2% 2.8%1.2% 0.8% 0.2% 1.4% 2.1% 0.7% Total 7.5% 33.1% 9.1% 8.0% 4.3% 11.6%15.5% 7.3%

TABLE 10 Screening 2 (cont'd), 300° C., 6 h Catalyst: 2-1 2-2 2-3 2-42-5 2-6 2-7 2-8 BDO Conversion 100.0% 77.8% 100.0% 100.0% 100.0% 100.0%100.0% 100.0% 1,3 butadiene 0.0% 0.1% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%butenes 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 4-vinyl-1- 0.2% 0.2%0.2% 0.2% 0.2% 0.3% 0.2% 0.2% cyclohexene acetone 0.0% 0.5% 0.0% 0.0%0.0% 0.2% 0.2% 0.0% isobutyraldehyde 0.0% 0.5% 0.0% 0.0% 0.0% 0.2% 0.2%0.0% 2,3-butanedione 0.2% 0.3% 0.3% 0.3% 0.2% 0.4% 0.3% 0.2% MEK 0.7%17.2% 1.3% 1.2% 0.8% 1.8% 1.8% 0.9% acetoin 0.5% 2.0% 1.5% 1.0% 0.5%1.8% 1.8% 0.8% MVC 3.1% 3.2% 2.0% 1.7% 0.0% 4.5% 3.9% 1.8% isobutanol0.2% 2.2% 1.0% 0.7% 0.1% 1.4% 1.4% 0.5% Total 4.8% 26.3% 6.3% 5.1% 1.9%10.4% 9.8% 4.4%

TABLE 11 Screening 2 (cont'd), 350° C., 3 h Catalyst: 2-1 2-2 2-3 2-42-5 2-6 2-7 2-8 BDO Conversion 100.0% 98.0% 95.7% 74.9% 100.0% 100.0%97.1% 92.5% 1,3 butadiene 0.1% 1.0% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1%butenes 0.1% 0.1% 0.0% 0.1% 0.1% 0.1% 0.1% 0.2% 4-vinyl-1- 2.0% 2.0%2.4% 2.6% 2.7% 2.8% 2.3% 1.6% cyclohexene acetone 0.5% 3.7% 2.6% 1.1%0.4% 2.9% 2.8% 1.3% isobutyraldehyde 0.5% 3.7% 2.6% 1.1% 0.4% 2.9% 2.8%1.3% 2,3-butanedione 0.9% 1.1% 1.3% 1.7% 1.3% 1.8% 1.9% 0.9% MEK 5.9%48.6% 21.5% 18.0% 6.9% 24.3% 24.8% 13.6% acetoin 3.6% 0.0% 0.0% 0.0%5.3% 0.0% 0.0% 0.0% MVC 13.3% 1.5% 0.9% 13.4% 1.3% 3.2% 3.8% 10.5%isobutanol 2.3% 8.0% 15.4% 9.3% 2.2% 17.5% 15.9% 9.1% Total 29.2% 69.7%46.8% 47.5% 20.6% 55.7% 54.5% 38.7%

TABLE 12 Screening 2 (cont'd), 350° C., 6 h Catalyst: 2-1 2-2 2-3 2-42-5 2-6 2-7 2-8 BDO Conversion 100.0% 100.0% 100.0% 100.0% 100.0% 100.0%100.0% 100.0% 1,3 butadiene 0.1% 0.7% 0.1% 0.1% 0.0% 0.1% 0.1% 0.1%butenes 0.1% 0.1% 0.0% 0.1% 0.1% 0.1% 0.1% 0.2% 4-vinyl-1- 0.2% 0.3%0.4% 0.3% 0.3% 0.5% 0.6% 0.2% cyclohexene acetone 0.4% 3.2% 2.0% 1.1%0.2% 2.6% 2.9% 0.9% isobutyraldehyde 0.4% 3.2% 2.0% 1.1% 0.2% 2.6% 2.9%0.9% 2,3-butanedione 0.7% 1.5% 1.1% 1.8% 1.1% 1.8% 2.4% 0.8% MEK 4.5%43.7% 16.0% 14.6% 5.0% 20.2% 23.6% 9.9% acetoin 2.4% 0.0% 0.0% 10.9%4.3% 0.0% 0.0% 7.2% MVC 9.0% 2.1% 8.3% 14.3% 1.1% 3.8% 4.8% 9.6%isobutanol 2.0% 8.6% 12.6% 9.0% 1.5% 16.7% 17.4% 6.7% Total 19.8% 63.5%42.5% 53.2% 13.8% 48.4% 54.7% 36.5%

TABLE 13 Screening 3, 350° C., 3 h Catalyst: 3-1 3-2 3-3 3-4 3-5 3-6 3-73-8 BDO Conversion 98.4% 88.7% 75.8% 84.2% 72.6% 89.7% 67.3% 75.6% 1,3butadiene 0.3% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% butenes 0.2% 0.1% 0.1%0.1% 0.1% 0.1% 0.1% 0.1% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% cyclohexene acetone 1.5% 2.4% 1.9% 2.5% 2.2% 2.3% 2.0% 2.0%isobutyraldehyde 2.5% 1.7% 0.5% 1.9% 1.0% 1.9% 0.5% 0.9% 2,3-butanedione0.0% 3.4% 2.4% 3.6% 3.4% 4.0% 3.2% 3.4% MEK 17.5% 21.7% 13.8% 21.2%15.7% 22.5% 14.7% 17.3% acetoin 3.6% 13.3% 10.5% 14.0% 11.9% 12.8% 12.1%12.2% MVC 2.2% 13.5% 8.7% 14.4% 12.0% 15.2% 12.3% 17.7% isobutanol 11.0%15.1% 8.2% 14.3% 9.6% 15.4% 8.6% 10.7% 2-butanol 2.2% 3.2% 2.5% 2.5%2.1% 3.0% 2.1% 1.6% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%unknown 2.2% 1.9% 1.3% 1.6% 1.3% 1.4% 1.0% 1.1% Total 38.9% 71.3% 46.2%72.1% 56.0% 74.4% 53.6% 64.4%

TABLE 14 Screening 3 (cont'd), 350° C., 6 h Catalyst: 3-1 3-2 3-3 3-43-5 3-6 3-7 3-8 BDO Conversion 95.2% 77.5% 61.9% 71.1% 59.9% 79.0% 53.6%60.6% 1,3 butadiene 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% butenes 0.1%0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% cyclohexene acetone 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% isobutyraldehyde 1.9% 1.4% 0.0% 1.4% 0.8% 1.6% 0.0% 0.7%2,3-butanedione 0.0% 3.4% 2.4% 3.6% 3.4% 4.1% 3.1% 3.3% MEK 11.4% 17.4%9.9% 16.8% 11.7% 19.4% 10.8% 14.0% acetoin 3.7% 16.3% 11.4% 15.5% 12.1%16.6% 12.0% 13.1% MVC 1.8% 14.8% 9.6% 15.0% 12.3% 17.2% 12.7% 18.9%isobutanol 8.1% 14.2% 7.7% 12.8% 8.6% 15.2% 7.8% 9.9% 2-butanol 1.6%2.5% 2.0% 1.9% 1.6% 2.4% 1.5% 1.3% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% unknown 1.1% 1.0% 0.4% 1.2% 0.8% 1.1% 0.6% 0.8% Total27.1% 67.6% 41.2% 65.3% 49.2% 74.2% 46.4% 60.0%

TABLE 15 Screening 3 (cont'd), 400° C., 3 h Catalyst: 3-1 3-2 3-3 3-43-5 3-6 3-7 3-8 BDO Conversion 100.0% 100.0% 100.0% 100.0% 100.0% 100.0%100.0% 100.0% 1,3 butadiene 2.4% 2.4% 2.4% 2.5% 7.5% 2.7% 2.0% 3.2%butenes 0.9% 1.0% 0.7% 1.0% 2.3% 1.3% 1.2% 1.2% 4-vinyl-1- 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.0% 0.0% cyclohexene acetone 0.0% 0.0% 0.0% 1.9%2.3% 2.1% 1.9% 1.7% isobutyraldehyde 6.8% 6.9% 6.5% 6.2% 5.7% 8.4% 7.4%9.0% 2,3-butanedione 0.0% 0.0% 0.0% 0.0% 0.0% 1.8% 2.1% 1.9% MEK 42.4%42.0% 41.6% 43.7% 40.6% 47.1% 43.9% 44.2% acetoin 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% 0.0% MVC 1.0% 1.4% 1.5% 1.2% 1.0% 1.7% 2.8% 2.2%isobutanol 9.0% 9.2% 7.6% 8.7% 5.1% 10.2% 8.7% 8.5% 2-butanol 2.0% 1.9%1.4% 1.9% 1.3% 1.9% 1.7% 1.3% 2-buteneol 0.9% 1.0% 0.0% 1.0% 0.8% 1.0%0.0% 0.0% unknown 1.3% 1.4% 1.6% 1.8% 1.9% 2.2% 2.3% 3.6% Total 62.5%62.9% 60.1% 65.2% 64.5% 75.4% 70.0% 71.9%

TABLE 16 Screening 3 (cont'd), 400° C., 6 h Catalyst: 3-1 3-2 3-3 3-43-5 3-6 3-7 3-8 BDO Conversion 100.0% 100.0% 100.0% 99.2% 100.0% 100.0%100.0% 100.0% 1,3 butadiene 2.2% 2.2% 2.3% 2.1% 3.9% 2.2% 1.9% 3.3%butenes 1.2% 1.1% 0.7% 1.1% 1.4% 1.2% 1.0% 1.2% 4-vinyl-1- 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.0% 0.0% cyclohexene acetone 0.8% 0.8% 0.6% 0.9%0.9% 0.9% 0.7% 0.6% isobutyraldehyde 10.9% 10.9% 9.7% 10.6% 8.3% 12.2%9.9% 11.1% 2,3-butanedione 3.0% 3.2% 2.5% 3.3% 1.7% 4.3% 3.4% 3.1% MEK47.4% 42.7% 42.9% 47.1% 39.2% 46.2% 42.3% 45.5% acetoin 0.0% 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.0% MVC 2.9% 3.3% 3.0% 4.1% 2.2% 4.9% 4.8% 5.3%isobutanol 11.4% 11.3% 9.9% 11.7% 6.5% 12.3% 10.8% 10.4% 2-butanol 1.6%1.6% 1.4% 1.7% 1.2% 1.6% 1.7% 1.1% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% unknown 4.0% 4.0% 3.4% 3.9% 4.0% 4.4% 3.5% 6.1% Total79.8% 75.6% 71.6% 80.8% 64.1% 84.2% 74.9% 80.5%

TABLE 17 Screening 4, 350° C., 3 h Catalyst: 4-1 4-2 4-3 4-4 4-5 4-6 4-74-8 BDO Conversion 72.1% 82.8% 82.8% 89.0% 87.8% 23.0% 33.2% 49.7% 1,3butadiene 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% butenes — — — — — — —— 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% cyclohexene acetone1.2% 1.3% 0.9% 0.9% 1.0% 1.2% 1.1% 1.0% isobutyraldehyde 1.5% 1.1% 0.8%0.0% 1.1% 0.0% 0.0% 0.4% 2,3-butanedione 3.1% 2.5% 2.6% 5.6% 5.7% 1.8%1.9% 2.2% MEK 11.4% 13.2% 11.3% 4.3% 7.1% 3.5% 3.2% 4.1% acetoin 13.1%8.5% 8.7% 5.9% 27.2% 2.8% 4.3% 7.6% MVC 9.2% 11.2% 12.7% 42.6% 19.5%1.2% 2.0% 7.3% isobutanol 11.8% 11.5% 9.9% 0.0% 2.4% 0.8% 0.8% 2.6%2-butanol 1.8% 2.6% 2.3% 0.0% 0.0% 0.0% 1.2% 2.2% 2-buteneol 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.0% 0.0% unknown — — — — — — — — Total 51.3% 49.3%46.8% 59.3% 64.1% 11.3% 13.3% 25.2%

TABLE 18 Screening 4 (cont'd), 350° C., 3 h Catalyst: 4-9 4-10 4-11 4-124-13 4-14 4-15 4-16 BDO Conversion 100.0% 39.2% 32.4% 34.8% 34.7% 16.3%62.2% 31.6% 1,3 butadiene 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%butenes — — — — — — — — 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 5.7%0.0% cyclohexene acetone 0.0% 1.3% 1.3% 1.4% 1.1% 1.3% 0.7% 1.0%isobutyraldehyde 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 1.3% 0.8% 2,3-butanedione0.0% 1.9% 1.7% 0.0% 1.6% 2.0% 0.0% 1.8% MEK 2.2% 1.8% 2.9% 1.3% 3.1%3.7% 21.6% 5.8% acetoin 0.0% 4.9% 1.9% 5.1% 0.0% 0.0% 0.0% 0.0% MVC 0.0%0.8% 0.0% 1.0% 1.0% 1.2% 0.0% 1.3% isobutanol 0.3% 0.7% 0.6% 0.4% 0.0%0.0% 0.0% 0.0% 2-butanol 0.0% 1.6% 0.0% 1.3% 0.0% 0.0% 0.0% 0.0%2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% unknown — — — — — — —— Total 2.5% 11.3% 8.4% 9.1% 6.8% 8.2% 29.2% 10.8%

TABLE 19 Screening 4 Repeat, 350° C., 3 h Catalyst: 4-1 4-2 4-3 4-4 4-54-6 4-7 4-8 BDO Conversion 83.9% 94.9% 83.4% 76.7% 82.5% 32.5% 29.3%43.2% 1,3 butadiene 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% Butenes 0.1%0.2% 0.2% 3.1% 0.6% 0.6% 0.6% 0.4% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% cyclohexene Acetone 1.7% 1.9% 1.3% 1.4% 1.5% 1.5% 1.6%1.6% isobutyraldehyde 3.3% 2.4% 1.0% 0.0% 1.3% 0.0% 0.0% 0.6%2,3-butanedione 2.2% 0.0% 2.3% 6.3% 4.8% 2.0% 2.1% 2.3% MEK 14.0% 17.6%11.1% 5.5% 8.0% 2.9% 2.9% 4.0% Acetoin 11.0% 2.6% 6.9% 5.3% 24.3% 2.6%4.3% 7.1% MVC 6.0% 6.9% 9.4% 29.9% 14.1% 1.0% 1.7% 5.9% isobutanol 14.3%14.5% 9.4% 0.0% 3.0% 0.6% 0.8% 2.8% 2-butanol 2.5% 3.4% 2.4% 0.0% 0.0%0.9% 1.4% 2.2% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% Total52.5% 46.1% 41.6% 51.4% 57.4% 11.2% 14.0% 24.9%

TABLE 20 Screening 4 Repeat (cont'd), 350° C., 3 h Catalyst: 4-9 4-104-11 4-12 4-13 4-14 4-15 4-16 BDO Conversion 51.7% 38.9% 33.2% 42.7%34.1% 21.2% 91.3% 19.8% 1,3 butadiene 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 1.5%0.0% Butenes 0.4% 0.7% 0.5% 0.5% 0.3% 0.3% 0.6% 1.0% 4-vinyl-1- 0.0%0.0% 0.0% 0.0% 0.0% 0.0% 3.9% 0.0% cyclohexene Acetone 1.8% 1.7% 1.4%1.7% 1.4% 1.6% 0.7% 1.5% isobutyraldehyde 0.0% 0.0% 0.0% 0.6% 0.0% 0.3%9.6% 1.3% 2,3-butanedione 2.1% 1.9% 1.7% 1.8% 1.7% 2.1% 0.0% 2.0% MEK6.5% 1.7% 2.7% 1.7% 4.2% 4.0% 49.8% 6.6% Acetoin 4.2% 4.2% 1.7% 4.9%0.0% 0.0% 0.0% 0.0% MVC 3.4% 0.0% 0.0% 0.7% 1.0% 1.0% 0.0% 1.2%isobutanol 1.8% 0.6% 0.5% 0.7% 0.0% 0.0% 0.0% 0.0% 2-butanol 1.9% 1.5%0.0% 1.7% 0.0% 0.0% 0.0% 0.0% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% unknown 0.5% 0.4% 0.1% 0.8% 0.5% 0.6% 5.4% 1.3% Total 20.1%10.8% 8.6% 12.4% 8.6% 9.3% 66.1% 13.6%

TABLE 21 Screening 4 Repeat (cont'd), 350° C., 6 h Catalyst: 4-1 4-2 4-34-4 4-5 4-6 4-7 4-8 BDO Conversion 80.1% 98.0% 51.1% 48.7% 65.2% — 49.8%18.3% 1,3 butadiene 0.3% 0.2% 0.3% 1.2% 0.4% 0.1% 0.3% 0.1% Butenes 0.2%0.4% 0.6% 4.5% 0.9% 1.1% 1.1% 0.8% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% cyclohexene Acetone 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% isobutyraldehyde 3.5% 0.0% 0.5% 0.0% 0.6% 0.0% 0.3% 0.0%2,3-butanedione 1.8% 0.0% 2.4% 4.5% 3.7% 0.0% 0.0% 2.0% MEK 14.5% 2.1%11.4% 5.1% 7.6% 2.3% 2.2% 3.6% Acetoin 9.4% 0.0% 10.2% 10.4% 27.4% 1.2%2.9% 6.1% MVC 4.2% 0.8% 11.8% 22.0% 14.9% 0.0% 0.0% 3.9% isobutanol13.5% 0.9% 8.9% 0.0% 2.9% 0.0% 0.6% 2.5% 2-butanol 2.2% 0.0% 2.2% 0.0%0.0% 0.0% 1.3% 1.5% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%unknown 1.6% 0.2% 0.6% 0.3% 0.6% 0.0% 0.4% 0.4% Total 47.5% 4.4% 46.2%47.7% 58.3% 4.8% 7.4% 19.2%

TABLE 22 Screening 4 Repeat (cont'd), 350° C., 6 h Catalyst: 4-9 4-104-11 4-12 4-13 4-14 4-15 4-16 BDO Conversion 26.8% 10.7% 46.4% 17.8%18.9% — 95.5% — 1,3 butadiene 0.1% 0.1% 0.2% 0.1% 0.4% 0.4% 14.1% 2.2%Butenes 0.7% 1.2% 1.0% 0.9% 0.4% 0.5% 0.6% 1.0% 4-vinyl-1- 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.6% 0.0% cyclohexene Acetone 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% 0.0% isobutyraldehyde 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 12.5%0.9% 2,3-butanedione 1.9% 0.0% 0.0% 0.0% 0.0% 1.9% 0.0% 2.0% MEK 5.3%1.3% 2.0% 1.1% 4.2% 3.8% 73.6% 7.3% Acetoin 3.9% 3.6% 1.4% 4.1% 0.0%0.0% 0.0% 0.0% MVC 1.9% 0.0% 0.0% 0.0% 0.8% 0.8% 0.0% 1.2% isobutanol1.3% 0.4% 0.0% 0.4% 0.0% 0.0% 0.0% 0.0% 2-butanol 1.7% 1.2% 0.0% 1.4%0.0% 0.0% 0.0% 0.0% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%unknown 0.1% 0.2% 0.1% 0.4% 0.3% 0.5% 6.9% 1.1% Total 15.1% 6.5% 4.6%6.6% 5.7% 7.4% 101.4% 14.7%

TABLE 23 Screening 5, 350° C., 3 h Catalyst: 5-1 5-2 5-3 5-4 5-5 5-6 5-75-8 BDO Conversion 84.2% 39.7% 41.5% 19.0% 41.4% 26.4% 24.9% 14.0% 1,3butadiene 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% Butenes 0.1% 0.3% 0.3%0.1% 0.2% 0.3% 0.3% 0.2% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% cyclohexene Acetone 1.9% 1.8% 1.5% 1.9% 1.6% 1.9% 1.8% 1.8%isobutyraldehyde 2.6% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 2,3-butanedione3.3% 1.7% 0.0% 1.9% 1.9% 2.0% 1.8% 2.0% MEK 15.5% 2.9% 2.9% 3.4% 2.5%3.1% 2.6% 4.3% acetoin 14.5% 4.5% 2.9% 2.6% 4.1% 2.7% 2.9% 0.8% MVC10.4% 1.2% 0.0% 0.0% 1.0% 0.8% 0.0% 0.0% isobutanol 15.1% 0.8% 0.6% 0.7%0.7% 0.7% 0.6% 0.0% 2-butanol 2.3% 1.3% 1.0% 0.0% 1.1% 0.0% 0.9% 0.0%2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% unknown 1.3% 0.3%0.2% 0.1% 0.3% 0.3% 0.2% 0.3% Total 63.3% 13.3% 8.2% 10.7% 12.0% 11.4%10.0% 9.1%

TABLE 24 Screening 5 (cont'd), 350° C., 3 h Catalyst: 5-9 5-10 65-115-12 5-13 5-14 5-15 5-16 BDO Conversion 15.4% 22.5% 34.1% 73.1% 43.4%76.6% 42.3% 45.7% 1,3 butadiene 0.0% 0.0% 0.0% 0.0% 0.0% 4.9% 0.0% 0.0%butenes 0.2% 0.1% 0.1% 0.2% 0.1% 14.1% 0.1% 0.5% 4-vinyl-1- 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.0% 0.0% cyclohexene acetone 2.3% 2.0% 1.7% 2.2%2.4% 1.9% 2.0% 1.6% isobutyraldehyde 0.0% 0.0% 0.0% 0.7% 0.0% 1.2% 0.0%0.0% 2,3-butanedione 1.9% 2.0% 1.9% 5.9% 2.5% 0.0% 3.2% 2.8% MEK 3.0%3.9% 2.8% 22.8% 10.1% 16.9% 10.3% 6.2% acetoin 2.9% 1.1% 3.4% 7.3% 5.0%1.5% 8.9% 5.9% MVC 0.0% 0.0% 1.0% 7.9% 0.0% 0.0% 10.9% 3.5% isobutanol0.6% 0.4% 0.7% 5.1% 1.5% 0.0% 6.1% 3.8% 2-butanol 0.0% 0.0% 1.0% 2.0%1.4% 1.1% 1.1% 1.0% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%unknown 0.2% 0.2% 0.2% 0.8% 0.5% 1.1% 0.5% 0.6% Total 10.8% 9.6% 11.7%52.2% 21.7% 40.6% 41.5% 24.3%

TABLE 25 Screening 5 (cont'd), 350° C., 6 h Catalyst: 5-1 5-2 5-3 5-45-5 5-6 5-7 5-8 BDO Conversion 70.6% 27.0% 23.2% 3.5% 18.4% 34.0% 9.2%1.7% 1,3 butadiene 0.1% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% butenes 0.1%0.4% 0.4% 0.2% 0.2% 0.3% 0.3% 0.2% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% cyclohexene acetone 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% isobutyraldehyde 1.8% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%2,3-butanedione 3.7% 0.0% 0.0% 0.0% 1.8% 0.0% 0.0% 0.0% MEK 15.3% 2.4%2.7% 2.7% 2.2% 1.7% 2.0% 3.4% acetoin 15.3% 3.9% 2.7% 2.0% 3.7% 2.8%2.5% 0.9% MVC 11.2% 1.1% 0.0% 0.0% 1.1% 0.0% 0.0% 0.0% isobutanol 12.9%0.4% 0.0% 0.0% 0.0% 0.4% 0.0% 0.0% 2-butanol 2.0% 0.9% 0.8% 0.0% 0.0%0.9% 0.0% 0.0% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%unknown 1.0% 0.2% 0.1% 0.1% 0.1% 0.3% 0.1% 0.1% Total 60.4% 8.2% 5.8%4.9% 9.0% 5.3% 4.9% 4.6%

TABLE 26 Screening 5 (cont'd), 350° C., 6 h Catalyst: 5-9 5-10 65-115-12 5-13 5-14 5-15 5-16 BDO Conversion 2.2% 5.6% 22.4% 57.4% 40.4%35.0% 31.9% 31.6% 1,3 butadiene 0.0% 0.0% 0.0% 0.2% 0.0% 3.1% 0.1% 0.1%butenes 0.2% 0.2% 0.1% 0.2% 0.1% 7.6% 0.1% 0.5% 4-vinyl-1- 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.0% 0.0% cyclohexene acetone 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% 0.0% isobutyraldehyde 0.0% 0.0% 0.0% 0.4% 0.0% 0.4% 0.0%0.0% 2,3-butanedione 0.0% 0.0% 0.0% 7.3% 2.2% 0.0% 3.0% 2.8% MEK 2.3%3.3% 2.3% 22.5% 10.4% 12.7% 10.6% 6.1% acetoin 2.4% 1.0% 2.7% 6.4% 5.1%1.5% 8.5% 5.4% MVC 0.0% 0.0% 0.9% 6.7% 0.0% 0.0% 11.7% 3.7% isobutanol0.0% 0.0% 0.4% 3.9% 1.0% 0.0% 5.4% 3.1% 2-butanol 0.0% 0.0% 0.0% 1.5%1.4% 0.0% 0.9% 0.0% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%unknown 0.1% 0.1% 0.1% 0.6% 0.4% 0.7% 0.4% 0.4% Total 5.0% 4.4% 6.4%47.6% 18.8% 25.4% 39.3% 21.6%

TABLE 27 Screening 6, 350° C., 3 h Catalyst: 6-1 6-2 6-3 6-4 6-5 6-6 6-76-8 BDO Conversion 80.0% 100.0% 55.7% 100.0% 70.3% 67.1% 69.4% 75.9% 1,3butadiene 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% butenes 0.1% 0.3% 0.2%4.0% 0.2% 0.2% 0.1% 0.1% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% cyclohexene acetone 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%isobutyraldehyde 1.4% 2.8% 0.0% 12.9% 0.0% 3.6% 0.7% 2.0%2,3-butanedione 3.2% 0.0% 1.8% 2.9% 2.1% 3.4% 2.7% 4.1% MEK 12.7% 31.5%5.0% 34.6% 5.3% 16.0% 8.9% 16.9% acetoin 14.4% 1.6% 4.0% 1.7% 6.8% 13.3%12.0% 18.3% MVC 10.9% 4.2% 7.3% 0.0% 5.1% 7.4% 7.5% 13.2% isobutanol13.4% 7.1% 3.0% 8.3% 5.1% 11.9% 10.3% 17.8% 2-butanol 2.0% 2.2% 0.0%0.0% 1.4% 0.0% 2.5% 2.7% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% unknown 1.9% 2.5% 0.4% 9.7% 1.2% 3.1% 1.4% 2.2% Total 56.2% 47.4%21.2% 64.4% 24.5% 55.8% 42.3% 72.3%

TABLE 28 Screening 6 (cont'd), 350° C., 3 h Catalyst: 6-9 6-10 6-11 6-126-13 6-14 6-15 6-16 BDO Conversion 27.1% 40.9% 88.7% 8.1% 25.7% 16.9%25.3% 19.5% 1,3 butadiene 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%butenes 0.1% 0.1% 0.3% 0.1% 0.1% 0.1% 0.1% 0.1% 4-vinyl-1- 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.0% 0.0% cyclohexene acetone 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% 0.0% isobutyraldehyde 0.0% 0.9% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 2,3-butanedione 2.7% 2.8% 0.0% 0.0% 0.0% 2.0% 0.0% 1.9% MEK 3.4%8.6% 2.6% 2.9% 2.8% 3.7% 3.9% 3.5% acetoin 3.9% 6.7% 2.5% 2.7% 2.7% 2.9%2.5% 2.3% MVC 4.4% 10.4% 4.1% 0.0% 0.9% 5.1% 4.7% 7.5% isobutanol 1.8%5.5% 0.0% 0.8% 0.9% 1.6% 1.4% 1.2% 2-butanol 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%unknown 0.4% 1.5% 0.2% 0.1% 0.2% 0.5% 0.5% 0.4% Total 16.3% 35.1% 9.5%6.6% 7.4% 15.5% 12.6% 16.4%

TABLE 29 Screening 6 (cont'd), 350° C., 6 h Catalyst: 6-1 6-2 6-3 6-46-5 6-6 6-7 6-8 BDO Conversion 64.0% 100.0% 39.7% 66.3% 53.5% 50.9%55.3% 62.6% 1,3 butadiene 0.1% 2.0% 0.1% 0.6% 0.1% 0.2% 0.1% 0.1%butenes 0.1% 0.3% 0.2% 0.8% 0.1% 0.2% 0.1% 0.1% 4-vinyl-1- 0.0% 0.0%0.0% 0.0% 0.0% 0.0% 0.0% 0.0% cyclohexene acetone 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% 0.0% isobutyraldehyde 1.0% 3.0% 0.0% 9.0% 0.0% 2.7% 0.4%1.3% 2,3-butanedione 3.8% 1.9% 0.0% 2.9% 2.4% 3.6% 2.8% 4.1% MEK 15.8%44.2% 6.1% 28.3% 6.7% 17.5% 10.9% 18.2% acetoin 15.8% 4.4% 3.8% 7.0%7.1% 12.0% 12.5% 17.2% MVC 13.0% 6.3% 8.0% 2.8% 5.9% 7.8% 8.3% 13.5%isobutanol 12.4% 7.2% 2.7% 6.8% 4.4% 9.6% 9.2% 13.9% 2-butanol 1.7% 1.9%0.0% 0.0% 1.2% 0.0% 2.2% 2.0% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% unknown 1.4% 3.0% 0.3% 7.6% 0.7% 2.7% 1.0% 1.7% Total 61.9%69.1% 20.9% 58.1% 26.8% 53.5% 44.4% 68.4%

TABLE 30 Screening 6 (cont'd), 350° C., 6 h Catalyst: 6-9 6-10 6-11 6-126-13 6-14 6-15 6-16 BDO Conversion 9.1% 34.1% 80.2% - 17.0% 8.4% 10.1%9.1% 1,3 butadiene 0.0% 0.1% 0.0% 0.0% 0.0% 0.0% 0.2% 0.0% butenes 0.1%0.1% 0.3% 0.1% 0.1% 0.1% 0.1% 0.1% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 0.0% cyclohexene acetone 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% isobutyraldehyde 0.0% 0.9% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%2,3-butanedione 2.7% 2.7% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% MEK 3.9% 10.1%2.9% 2.7% 2.6% 3.9% 4.5% 3.8% acetoin 3.6% 6.4% 3.0% 2.1% 2.2% 2.4% 2.2%1.8% MVC 4.9% 11.2% 3.3% 0.0% 1.0% 5.4% 5.5% 7.9% isobutanol 1.5% 5.0%0.0% 0.4% 0.5% 1.2% 1.0% 0.8% 2-butanol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%0.0% 0.0% 2-buteneol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% unknown0.2% 1.4% 0.1% 0.1% 0.1% 0.4% 0.4% 0.3% Total 16.9% 36.5% 9.5% 5.3% 6.4%13.0% 13.4% 14.4%

TABLE 31 Screening 7, 300° C., 3 h Catalyst: 7-1 7-2 7-4 7-7 7-8 MVCConversion 16.4% 73.8% 62.2% 98.4% 51.3% 1,3 butadiene 6.6% 17.7% 25.9%65.6% 56.6% butenes 0.0% 0.1% 0.1% 0.9% 0.4% 4-vinyl-1- 0.0% 0.3% 0.4%0.0% 0.0% cyclohexene acetone 0.0% 0.0% 0.0% 0.0% 0.0% isobutyraldehyde0.0% 0.0% 0.0% 0.0% 0.0% 2,3-butanedione 0.0% 0.0% 0.0% 0.0% 0.0% MEK0.0% 0.0% 0.0% 0.0% 0.0% acetoin 0.0% 0.0% 0.0% 0.0% 0.0% isobutanol0.0% 0.0% 0.0% 0.0% 0.0% 2-butanol 1.2% 0.6% 0.8% 0.0% 1.4% 2-buteneol3.6% 1.4% 1.3% 0.0% 4.2% unknown 0.0% 0.0% 0.0% 0.0% 0.1% Total 6.6%18.2% 26.3% 66.6% 57.0%

TABLE 32 Screening 7 (cont'd), 300° C., 3 h Catalyst: 7-11 7-12 7-137-14 7-15 7-16 MVC 100.0% 75.3% 100.0% 67.7% 100.0% 100.0% Conversion1,3 butadiene 3.9% 69.5% 118.0% 46.4% 59.8% 16.3% butenes 148.9% 1.1%2.6% 0.8% 2.5% 0.8% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% cyclohexeneacetone 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% isobutyral- 0.0% 0.0% 0.0% 0.0%0.0% 0.0% dehyde 2,3- 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% butanedione MEK 0.8%0.7% 0.6% 0.6% 3.7% 1.0% acetoin 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%isobutanol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 2-butanol 0.0% 0.7% 0.0% 0.7%0.0% 0.0% 2-buteneol 0.0% 1.7% 0.0% 1.7% 0.0% 0.0% unknown 0.1% 0.1%0.1% 0.1% 0.4% 0.0% Total 153.5% 71.4% 121.3% 47.9% 65.9% 18.2%

TABLE 33 Screening 7 (cont'd), 400° C., 3 h Catalyst: 7-1 7-2 7-4 7-77-8 MVC Conversion 26.9% 81.8% 67.8% 100.0% 46.0% 1,3 butadiene 19.0%17.4% 46.7% 55.7% 116.0% butenes 0.4% 0.9% 1.6% 2.1% 2.8% 4-vinyl-1-0.0% 0.0% 0.0% 0.0% 0.0% cyclohexene acetone 0.0% 0.0% 0.0% 0.0% 0.0%isobutyraldehyde 0.0% 0.0% 0.0% 0.0% 0.0% 2,3-butanedione 0.0% 0.0% 0.0%0.0% 0.0% MEK 0.0% 0.0% 0.0% 0.0% 0.7% acetoin 0.0% 0.0% 0.0% 0.0% 0.0%isobutanol 0.0% 0.0% 0.0% 0.0% 0.0% 2-butanol 1.0% 0.0% 0.6% 0.0% 1.1%2-buteneol 0.7% 0.0% 0.0% 0.0% 1.7% unknown 0.0% 0.0% 0.0% 0.0% 0.0%Total 19.4% 18.4% 48.2% 57.8% 119.4%

TABLE 34 Screening 7 (cont'd), 400° C., 3 h Catalyst: 7-11 7-12 7-137-14 7-15 7-16 MVC 100.0% 41.3% 100.0% 36.3% 100.0% 100.0% Conversion1,3 butadiene 116.2% 72.2% 99.0% 32.2% 72.4% 13.4% butenes 6.7% 1.7%7.0% 1.0% 3.3% 1.2% 4-vinyl-1- 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% cyclohexeneacetone 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% isobutyral- 0.0% 0.0% 0.0% 0.0%0.0% 0.0% dehyde 2,3- 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% butanedione MEK 0.7%0.0% 0.6% 0.0% 1.4% 0.0% acetoin 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%isobutanol 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 2-butanol 0.0% 1.2% 0.0% 1.1%0.0% 0.0% 2-buteneol 0.0% 1.5% 0.0% 1.1% 0.0% 0.0% unknown 0.1% 0.0%0.1% 0.0% 0.1% 0.0% Total 123.6% 73.9% 106.5% 33.2% 77.1% 14.6%

Example 3 Flow Reactor Evaluation of Catalysts

A small, continuous fixed bed flow reactor (FIG. 1) was constructed toinvestigate chemical conversions on a scale larger than those in thepyroprobe and high throughput tests with control of feed rates,temperatures, and pressures. An Isco high-pressure syringe pump 20(Teledyne Isco, Lincoln, Nebr.) was used to deliver neat or aqueous BDO10 through a preheater 30 to a ⅜″ outer diameter stainless steel reactortube 40. The tube 40 was packed with 0.5-3.5 g catalyst with glass beadsabove the bed for feed preheating. When about 0.5 g catalyst was used,the catalyst bed volume was about 0.6 cc with a bed length of about 0.5″(1.3 cm). In₂O₃, La-doped ZrO₂ (XZ0945/03), and mixed Al/La/Zr oxide(FZO2089) catalysts were evaluated. For this example, the In₂O₃catalyst, from the oxalic acid preparation, was prepared by oxalatedecomposition, and calcined at 550° C. for 6 h in air prior to loading.Thermocouples 35, 45 were positioned to measure the temperature of thevapor space and the catalyst bottom, respectively. The liquid feed flowrate was 0.05 mL/min and an inert carrier gas (N₂ or Ar) 50 wasdelivered at 39 cc/min. using a mass flow controller 60. The reactorpressure was nominally 1 atm absolute. A product trap 70 and flow meter80 were positioned downstream from the reactor tube 40. Testing wasvaried between 225° C. and 425° C. All samples were collected andanalyzed as in Example 2 except that gas samples were withdrawn 75 andinjected manually.

Results are shown in Table 35. The In₂O₃ catalyst was more selective forMVC than the Brønsted-acidic catalysts tested. MEK selectivity wasgenerally much lower than with the other catalysts.

TABLE 35 Conversion of BDO (near except where noted) in a Flow ReactorGas W/F Cat. MHSV Flow (g · cat)- ³BDO BD BD MVC MVC MEK MEK AcetoinAcetoin Mass C Mass g BDO/ mL/ hr/total T Conv. Yield Sel Yield SelYield Sel Yield Sel Bal Bal Run ⁴Cat. g g · cat/hr min mol ° C. % % % %% % % % % % % ¹11 FZO 3.47 0.07 9.5 66.0 250 100 6 8 0 0 94 94 — — 100 —2089 300 100 11 15 0 0 89 89 — — 96 — ¹13 FZO 3.47 0.07 9.5 66.0 350 10024 24 0 0 72 72 — — 101 87 2089 400 100 9 9 0 0 19 19 — — 97 32 300 1007 7 0 0 84 84 — — 97 97 ²17 FZO 3.51 0.62 9.8 1.5 250 — 0.4 — — — — — —— 98 — 2089 300 — 5.4 — — — — — — — 95 — 350 — 7.7 — — — — — — — 97 —400 — 6.8 — — — — — — — 104 — 300 — 4.8 — — — — — — — 100 — 21 FZO 3.510.86 10 60.1 350 — 2.3 — — — — — — — 74 — 2089 20 42.2 — 2.6 — — — — — —— 84 — 30 32.5 — 2.6 — — — — — — — 79 — 24 FZO 0.52 5.77 100 1.9 350 681.4 2.1 0 0 38.7 56.9 9.7 14.3 89 98 2089 30 4.8 79 1.9 2.4 2.4 3.0 29.737.6 8.4 10.6 99 77 10 9.0 97 1.1 1.1 0 0 8.7 9.0 2.1 2.2 97 18 27 XZ00.5 6.00 100 1.8 300 4 0 0.0 3.5 87.5 3.7 92.5 3.2 80.0 103 108 945/03100 1.8 350 91 0 0.0 12.9 14.2 20.8 22.9 8.2 9.0 94 65 30 4.6 350 90 00.0 12.7 14.1 23.4 26.0 10.5 11.7 98 74 29 XZ0 0.5 6.00 30 4.6 350 93 00.0 13 14.0 29.2 31.4 11.6 12.5 96 85 945/03 400 100 5.9 5.9 1.5 1.5 4646.0 0 0 96 80 425 100 7.9 7.9 0 0 42.9 42.9 0 0 96 78 ²32 XZ0 0.5 0.3030 2.1 350 100 2 2 6 6 93 93 0 0 99 — 945/03 400 100 16.2 16.2 0 0 58.458.4 0 0 99 93 425 100 11.3 11.3 0 0 45.7 45.7 0 0 97 70 35 XZ0 0.5 6.0030 4.6 350 95 0 0 7.9 8.3 29.2 30.7 11 11.6 97 79 945/03 400 100 1.8 1.81.3 1.3 42.9 42.9 0 0 97 73 425 100 3.0 3.0 0 0 47.2 47.2 0 0 96 77 39In₂O₃ 0.5 6.00 30 4.6 350 92 2.9 3.2 41.4 45.0 6.6 7.2 6.3 6.8 98 82 400100 1.1 1.1 8.4 8.4 28.1 28.1 7.5 7.5 100 79 425 100 0.7 0.7 4.6 4.632.8 32.8 7.4 7.4 100 83 ²42 In₂O₃ 0.5 0.30 30 2.1 350 94 0 0 8.7 9.320.2 21.5 20.2 21.5 99 65 400 100 0 0 5.6 5.6 29 29.0 0 0 99 64 425 1000 0 6.2 6.2 18.7 18.7 0 0 102 42 45 In₂O₃ 0.5 6.00 39 3.8 300 56 0 036.9 65.9 1.1 2.0 11.1 19.8 98 94 315 80 0.4 0.5 47.2 59.0 2.4 3.0 9.612.0 87 84 330 93 1.5 1.6 50.8 54.6 4.7 5.1 5.8 6.2 101 81 350 98 4 4.139.6 40.4 7.8 8.0 0.8 0.8 98 70 48 In₂O₃ 0.5 6.12 30 4.6 225 0 0 0 0 0 00 0 0 97 100 250 3.9 0 0 2.8 71.8 0 0 1.1 28.2 98 105 275 20 0 0 12.663.0 0 0 5.3 26.5 98 98 300 49 0 0 32.7 66.7 0.9 1.8 11.9 24.3 101 98²55 In₂O₃ 0.51 0.30 30.5 2.2 250 11 0 0 3.5 31.8 0 0 5.4 49.1 100 100300 85 0 0 15.1 17.8 2.2 2.6 10.4 12.2 95 48 350 97 5.2 5.4 9.1 9.4 6.56.7 0 0 86 46 57 In₂O₃ 0.51 6.00 32.3 4.5 250 2.2 0 0 0 0 0 0 1.9 86.4104 109 300 39 0.4 1.0 20 51.3 1.3 3.3 14.4 36.9 100 100 350 89 1.8 2.037 41.6 7.2 8.1 10 11.2 97 88 250 2 0 0 0.3 15.0 0 0 1.3 65.0 100 100 60In₂O₃ 0.5 6.02 31.6 4.5 250 3 0 0 2.0 66.7 0 0 1 33 100 — 300 59 0.4 0.741.3 70.0 1.7 2.9 9.7 16.4 98 100 350 92 3.2 3.5 39.6 43.0 9 9.8 8.4 9.196 93 63 In₂O₃ 0.5 6.12 29.7 4.6 250 10 0.0 0.0 1.8 18.0 0.0 0.0 2.121.0 97 95 300 59 0.0 0.0 26.2 44.4 2.2 3.7 12.1 20.5 98 87 350 97 0.00.0 36.5 37.6 10.0 10.3 3.1 3.2 93 75 66 Ga₂O₃ 0.5 6.12 32.1 4.4 250 460.0 0.0 1.8 3.9 11.4 24.8 1.0 2.2 99 71 300 100 12.5 12.5 0.0 0.0 65.865.8 0.5 0.5 100 95 350 100 7.1 7.1 0.0 0.0 63.5 63.5 0.5 0.5 96 94 6910% 0.5 6.00 31 4.5 250 13 0.0 0.0 0.0 0.0 0.1 0.8 0.3 2.3 100 90 In₂O₃/300 16 0.0 0.0 0.9 5.6 0.7 4.4 2.6 16.3 101 91 Silica 350 45 0.0 0.0 4.08.9 5.2 11.6 18.8 41.8 98 89 75 10% 0.5 6.24 30.2 4.6 250 11 0.0 0.0 1.110.0 0.0 0.0 0.5 4.5 100 92 SnO₂/ 300 34 0.0 0.0 14.4 42.4 0.5 1.5 4.312.6 96 87 In₂O₃ 350 42 0.0 0.0 11.8 28.1 2.9 6.9 11.2 26.7 96 90 80 10%0.5 6.00 30.7 4.6 250 15 0.0 0.0 0.0 0.0 0.0 0.0 4.1 27.3 99 90 In₂O₃/300 26 0.0 0.0 2.6 10.0 2.1 8.1 17.4 66.9 101 101 Hyperion 350 80 0.00.0 12.8 16.0 11.1 13.9 37.3 46.6 98 100 83 MEL 0.52 5.88 32.9 4.5 250 40.0 0.0 0.0 0.0 0.0 0.0 0.8 20.0 106 97 0802/ 300 20 0.0 0.0 1.4 7.0 1.68.0 2.7 13.5 98 86 03 350 71 0.0 0.0 12.1 17.0 21.9 30.8 16.8 23.7 99 9985 MEL 0.5 6.06 32.6 4.4 250 10 0.0 0.0 0.0 0.0 0.0 0.0 1.0 10.0 100 91XZ0 300 19 0.0 0.0 2.9 15.3 3.1 16.3 4.4 23.2 96 93 945/03 350 98 0.00.0 14.1 14.4 27.1 27.7 19.5 19.9 96 106 ¹0.1 mL/min dodecane co-fed ²5wt % BDO water ³Products were collected in diglyme for Runs 24 to 85⁴In₂O₃ by oxalic acid precipitation method

Example 4 Flow Reactor Evaluation of Al/La/Zr Oxide Catalyst

An apparatus similar to that described in Example 3 was used. Theprocess flow diagram is shown in FIG. 2. An isocratic HPLC pump 120 wasused to introduce liquid feeds 110, including neat and aqueous BDO. Thereactor 140 was made of stainless steel tubing with ¼″ outer diameter.The catalyst bed was positioned approximately in the middle of the tube,held in place by quartz wool plugs and 80-100 mesh Pyrex® glass beads,both above (for feed preheating) and below the catalyst bed. The packedreactor tube 140 was placed approximately in the middle of anelectrically heated furnace. The furnace control thermocouple 145 waslocated on the outside skin of the reactor tube, adjacent to thecatalyst bed. A preheater 130 and thermocouple were located upstreamfrom the reactor tube 140. A mass flow controller 160 was used tocontrol nitrogen, air, or H₂ carrier gases 150 at flow rates up to 1000sccm. The system also included a condenser 170 and two chilled receivervessels 180, 190 for collecting liquid product samples alternatelywithout disturbing the run. Effluent gas rates were measured with a soapbubble flow meter 210 and stopwatch and gas samples 200 obtained using agas-tight syringe. Gas samples were analyzed on a Carle Series 400 AGCusing the #160-Sp application (refinery gas analysis). Liquid sampleswere analyzed on an Agilent 6890 GC with an FID detector or on theAgilent GC/MS described above.

In this example, the catalyst was powdered FZO2089 prepared by MELChemicals, Inc. The FZO2089 material is a proprietary mixed oxidepreparation of aluminum, lanthanum, and zirconium. A portion of thepowdered material was first pelletized, then ground and sieved to a60-100 mesh size fraction that could be run in the flow reactor. Thismaterial had an apparent bulk density of 1.0924 g/cm³ and 0.5472 g(˜0.5009 cm³) was loaded into the reactor for testing.

The feedstock solution used was either a 50 wt % solution of BDO(Aldrich) in deionized water or neat BDO (Aldrich). The flow reactorresults are shown in Table 36. The highest 1,3BD yields were observed atthe lowest reaction temperatures investigated near the end of thetesting. It should be noted that a catalyst regeneration step was notimplemented during the first 3 runs, but was shown to be beneficial insubsequent runs.

The 1,3BD determinations were based entirely on gas phase analyses,which reported moles of product. Therefore, yields were estimated as apercentage of total BDO fed. Because some 1,3BD was detected in theliquid phase, which was not quantified, the 1,3BD yields reported areconsidered to be conservative. Estimated yields were lower in the flowreactor than in the pyroprobe. The difference may be attributable to theamount of water in the feed and/or the degree of 1,3BD oligomerizationon the catalyst.

TABLE 36 Flow reactor results for the conversion of BDO to 1,3BD Liq.Feed Contact Run Feed N₂ Gas Flow Rate, Time, T, 1,3 BD # CompositionRate, sccm mL/h msec ° C. % Yield 1  50% BDO 26.0 3 185 450 7.93 2  50%BDO 50.5 3 126 500 3.49 3  50% BDO 26.0 3 173 500 3.93 4* 50% BDO 26.0 3173 500 5.74 5* Neat BDO 51.4 3 189 450 3.77 6* Neat BDO 50.6 3 206 4008.82 7* Neat BDO 101.6 3 114 400 8.33 *Catalyst regenerated by heatingto 500° C. in air overnight prior to this run

Example 5 Flow Reactor Evaluation of In₂O₃ Catalysts Prepared by theAmmonium Oxalate Precipitation Method

Experiments were conducted using the In₂O₃ catalyst prepared using theammonium oxalate method. Testing was conducted in the same apparatus andusing the same methods described in Example 3.

Results are shown in Table 37. While the Li-doped material did not havegood selectivity, the undoped In₂O₃ provided MVC selectivities (about80%) superior to other materials tested and low selectivities to MEK(1-3%). Of the temperatures tested, the highest selectivity was obtainedat 300° C. Performance was stable at this temperature for at least 470min TOS. Doubling the catalyst loading from 0.5 to 1 g increasedselectivity to MVC but had a marginal effect on BDO conversion. Notethat the blank experiment shows that the reactor tube and pre-heaterpacking material without any catalyst had a small activity for BDOdehydrogenation at 350° C.

In view of the many possible embodiments to which the principles of thedisclosed invention may be applied, it should be recognized that theillustrated embodiments are only preferred examples of the invention andshould not be taken as limiting the scope of the invention. Rather, thescope of the invention is defined by the following claims. We thereforeclaim as our invention all that comes within the scope and spirit ofthese claims.

TABLE 37 Conversion of Neat BDO in a Flow Reactor Using In₂O₃ CatalystsSynthesized from the Ammonium Oxalate Preparation MHSV Gas W/F, Cat. gBDO/ Flow (g · cat)- ²BDO BD MVC MEK Mass Mass g · mL/ hr/total T Tos,Conv. Yield BD Yield MVC Yield MEK Acetoin Acetoin Bal C Bal Run ¹Cat. gcat/hr min mol ° C. min % % Sel % % Sel % % Sel % Yield % Sel % % % 7210% 0.5 6.00 31.7 4.5 250 — 11 0.0 0.0 0.0 0.0 0.0 0.0 0.4 3.6 99 91 Li/300 — 13 0.0 0.0 0.0 0.0 0.4 3.1 6.0 46.2 106 95 In₂O₃ 350 — 57 0.0 0.00.0 0.0 2.0 3.5 23.0 40.4 98 73 77 In₂O₃ 0.5 6.00 31.9 4.5 250 — 5 0.00.0 3.5 69.9 0.05 1.0 0.4 7.8 105 105 300 — 79 0.0 0.0 52.5 66.5 2.4 3.06.5 8.2 102 91 350 — 100 6.2 6.2 46.8 46.8 7.1 7.1 1.1 1.1 100 88 88In₂O₃ 0.95 3.16 31.9 8.5 250 — 16 0.0 0.0 11.1 69.4 0.0 0.0 3.0 18.8 10098 300 — 86 3.5 4.1 64.2 74.7 3.3 3.8 9.0 10.5 101 104 350 — 97 27.428.2 42.2 43.5 5.7 5.9 0.0 0.0 97 102 91 In₂O₃ 1.01 2.97 32.2 8.9 300198 71 0.0 0.0 57.6 81.1 1.1 1.5 7.7 10.8 98 96 380 67 0.0 0.0 54.5 81.31.0 1.5 7.6 11.3 98 98 470 63 0.0 0.0 52.5 83.3 0.0 0.0 7.2 11.4 99 9798 None 0.0 — 32.2 0.0 300 — 4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 98 96 350— 10 0.0 0.0 0.0 0.0 0.0 0.0 6.1 61.0 101 96 ¹In₂O₃ by oxalic acidprecipitation method ²Products were collected in diglyme

We claim:
 1. A method, comprising: converting 2,3-butanediol to methylvinyl carbinol, 1,3-butadiene, or a mixture thereof by contacting a feedstream comprising 2,3-butanediol with a catalyst comprising (a)M_(x)O_(y) where M is a rare earth metal, a group IIIA metal, Zr, or acombination thereof, and x and y have values based upon an oxidationstate of M, and wherein the catalyst is not CeO₂, or (b) M³_(a)(PO₄)_(b) where M³ is a group IA metal, a group IIA metal, a groupIIIA metal, or a combination thereof, and a and b have values based uponthe oxidation state of M³; and dehydrating at least a portion of the2,3-butanediol to form a product comprising methyl vinyl carbinol,1,3-butadiene, or a combination thereof.
 2. The method of claim 1,wherein the catalyst has a methyl vinyl carbinol selectivity of at least20%, a 1,3-butadiene selectivity of at least 20%, or a combined1,3-butadiene and methyl vinyl carbinol selectivity of at least 20%. 3.The method of claim 1, wherein M is In, Sc, La, Tm, or a combinationthereof.
 4. The method of claim 1, wherein the catalyst furthercomprises a dopant M², wherein M² is a rare earth metal, a group IAmetal, a group IIA metal, a group IIIA metal, Zr, or a combinationthereof, and wherein M² is different than M or M³.
 5. The method ofclaim 5, wherein M is Zr.
 6. The method of claim 1, wherein the catalystis (i) an oxide of In, Al, La, and Zr, (ii) an oxide of Al and Zr, (iii)an oxide of Zr and Ca, (iv) Tm₂O₃, (v) ZrO₂, (vi) Sc₂O₃, or (vii) In₂O₃.7. The method of claim 1, wherein the catalyst is In₂O₃.
 8. The methodof claim 1, wherein the feed stream is contacted with the catalyst at atemperature within a range of 250° C. to 700° C. and atmosphericpressure.
 9. The method of claim 1, wherein the feed stream is contactedwith the catalyst at a flow rate effective to produce a W/F (catalystweight (g)/feed flow rate (mol/h)) value within a range of 0.5 to 100 gcatalyst·h/mol feed stream.
 10. The method of claim 9, wherein the W/Fvalue is from 1 to 10 g catalyst·h/mol feed stream.
 11. The method ofclaim 1, wherein at least 5% of the 2,3-butanediol is dehydrated. 12.The method of claim 1, wherein the catalyst is disposed within a column,and the method further comprises flowing the feed stream through thecolumn at a weight hourly space velocity from 0.3 to 12 h⁻¹.
 13. Themethod of claim 1, wherein the product comprises methyl vinyl carbinol,and the method further comprises: contacting the product comprisingmethyl vinyl carbinol with a solid acid catalyst; and dehydrating atleast a portion of the methyl vinyl carbinol to 1,3-butadiene.
 14. Themethod of claim 13, wherein the solid acid catalyst is analuminosilicate, alumina, sulfated zirconia, or a mixture thereof.
 15. Amethod, comprising: converting 2,3-butanediol to 1,3-butadiene bycontacting a feed stream comprising 2,3-butanediol with a first catalystat a temperature within a range of 250° C. to 700° C., wherein the firstcatalyst comprises M_(x)O_(y) where M is a rare earth metal, a groupIIIA metal, Zr, or a combination thereof, and x and y have values basedupon an oxidation state of M, and wherein the catalyst is not CeO₂;dehydrating at least 5% of the 2,3-butanediol in the feed stream withthe first catalyst to form a first product comprising methyl vinylcarbinol, 1,3-butadiene, or a combination thereof; contacting the firstproduct with a second catalyst comprising a solid acid catalyst at atemperature from about 250° C. to about 700° C.; and dehydrating atleast 5 wt % of the methyl vinyl carbinol to form a second productcomprising 1,3-butadiene.
 16. The method of claim 15, wherein M is In,Sc, La, Tm, or a combination thereof.
 17. The method of claim 15,wherein the first catalyst further comprises M², wherein M² is a rareearth metal, a group IA metal, a group IIA metal, a group IIIA metal,Zr, or a combination thereof, and wherein M² is different than M. 18.The method of claim 15, wherein the first catalyst is In₂O₃.
 19. Themethod of claim 15, wherein at least 50% of the 2,3-butanediol in thefeed stream is dehydrated with the first catalyst.
 20. The method ofclaim 19, wherein the solid acid catalyst is an aluminosilicate,alumina, sulfated zirconia, or a mixture thereof.